Terminal-modified difunctional sulfur-containing polymers, compositions thereof and methods of use

ABSTRACT

Disclosed are terminal-modified difunctional sulfur-containing polymers that are the reaction products of a sulfur-containing diol, an aldehyde or a ketone, and a compound containing a functional group. Compositions comprising the terminal-modified difunctional sulfur-containing polymers useful as sealants are also disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation application of U.S. patentapplication Ser. No. 14/133,679, filed Dec. 19, 2013, which is acontinuation application of U.S. patent application Ser. No. 13/950,668filed Jul. 25, 2013, and issued as U.S. Pat. No. 8,680,214 on Mar. 25,2014, which is a divisional application of U.S. patent application Ser.No. 13/050,988 filed Mar. 18, 2011, and issued as U.S. Pat. No.8,541,513 on Sep. 24, 2013.

FIELD

The present disclosure relates to terminal-modified difunctionalsulfur-containing polymers, compositions comprising terminal-modifieddifunctional sulfur-containing polymers, and methods of usingterminal-modified difunctional sulfur-containing polymers.

BACKGROUND

Thiol-terminated sulfur-containing polymers are known to be well-suitedfor use in various applications such as aerospace sealant compositions,due, in large part, to their fuel-resistance. Other desirable propertiesfor aerospace sealant compositions include low temperature flexibility,short curing time (the time required to reach a predetermined strength),and elevated-temperature resistance, among others. Sealant compositionsexhibiting at least some of these characteristics and containingthiol-terminated sulfur-containing polymers are described, for example,in U.S. Pat. Nos. 2,466,963, 4,366,307, 4,609,762, 5,225,472, 5,912,319,5,959,071, 6,172,179, 6,232,401, 6,372,849, and 6,509,418.Polythioethers that are liquid at room temperature and pressure and thathave excellent low temperature flexibility and fuel resistance, such asthose disclosed in U.S. Pat. No. 6,172,179, are also useful in aerospacesealant applications. For example, difunctional polythioethers havingterminal hydroxyl groups prepared by reacting a hydroxyl compound withan aldehyde are described, in GB 850,178, U.S. Pat. Nos. 3,290,382,3,959,227, and 3,997,614. Difunctional polythioethers terminated orcapped with isocyanates are also known as disclosed, for example, in GB850,178, and in U.S. Pat. Nos. 3,290,382, 3,959,227, and 3,997,614.

Polysulfides are also used in aerospace sealant applications where theyprovide high tensile strength, high shear strength, high-temperaturethermal resistance, and fuel resistance, as disclosed, for example inU.S. Pat. No. 7,638,162 and U.S. Publication No. 2005/0245695.

SUMMARY

Sulfur-containing polymers terminated with other functional groups canenable the use of alternative curing chemistries and can providesealants having enhanced properties suitable for aerospace sealantapplications.

In a first aspect of the present disclosure, terminal-modifiedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising: (a) a sulfur-containing polymer of Formula (I):

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and (b) a compound comprising a terminal group selected from a vinylgroup, a silyl group, and an epoxy group; and a group selected from agroup that is reactive with the terminal hydroxyl groups of the polymerof Formula (I).

In a second aspect of the present disclosure, terminal-modifiedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising: (a) and (b), wherein (a) comprises the reactionproducts of reactants comprising: (i) and (ii), wherein (i) comprises asulfur-containing polymer of Formula (I), wherein n is an integerselected from 1 to 50; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; and each R² isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and (ii) comprises a first compoundselected from a diisocyanate, an ethylenically unsaturated isocyanate,and a tosylate; and (b) comprises a second compound comprising aterminal group selected from a vinyl group, a silyl group, and an epoxygroup; and a group selected from a group that is reactive with anisocyanate group, an ethylenically unsaturated group, and a tosylate.

In a third aspect of the present disclosure, amine-terminatedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising: (a) and (b), wherein (a) comprises the reactionproducts of reactants comprising (i) and (ii), wherein (i) comprises asulfur-containing polymer of Formula (I), wherein n is an integerselected from 1 to 50; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; and each R² isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and (ii) comprises a first compoundselected from a diisocyanate, an activated ethylenically unsaturatedisocyanate, and a tosylate; and (b) comprises a second compoundcomprising an amine group and a group selected from a group that isreactive with an isocyanate group, an ethylenically unsaturated group,and a tosylate.

In a fourth aspect of the present disclosure, thiol-terminatedsulfur-containing polymers are provided comprising the reaction productsof reactants comprising: (a) and (b), wherein (a) comprises the reactionproducts of reactants comprising (i) and (ii), wherein (i) comprises asulfur-containing polymer of Formula (I), wherein n is an integerselected from 1 to 50; each p is independently selected from 1 and 2;each R¹ is independently selected from C₂₋₆ alkanediyl; and each R² isindependently selected from hydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl,substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂aryl, and substituted C₆₋₁₂ aryl; and (ii) comprises a first compoundselected from a diisocyanate, thiourea, an ethylenically unsaturatedisocyanate, and a tosylate; and (b) comprises a mercaptoalkanol when(ii) comprises a diisocyanate; a metal hydrosulfide when (ii) comprisesthiourea; a dithiol when (ii) comprises an ethylenically unsaturatedisocyanate; and a metal hydrosulfide when (ii) comprises a tosylate.

In a fifth aspect of the present disclosure, terminal-modifiedsulfur-containing polymers of Formula (II) are provided:

wherein n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂-phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and each R³ is —OR^(3′) wherein R^(3′) is independently selected from avinyl-terminated group, a silyl-terminated group, an amine-terminatedgroup, an epoxy-terminated group, and a thiol-terminated group.

In a sixth aspect of the present disclosure, amine-terminatedsulfur-containing polymers of Formula (III) are provided:

wherein n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₂₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and each R⁶ is independently selected from hydrogen, C₅₋₆ cycloalkyl,phenyl, and C₁₋₆ alkyl.

In a seventh aspect of the present disclosure, thiol-terminatedsulfur-containing polymers of Formula (IVa) and Formula (IVb) areprovided:

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and each R⁶ is independently selected from C₁₋₆ alkanediyl and C₅₋₁₂heteroalkanediyl.

In an eighth aspect of the present disclosure, compositions are providedcomprising a terminal-modified sulfur-containing polymer provided by thepresent disclosure and a curing agent that is reactive with theterminal-modified sulfur-containing polymer.

In a ninth aspect of the present disclosure, apertures are provided thatare sealed with a sealant comprising a composition comprising aterminal-modified sulfur-containing polymer provided by the presentdisclosure and a curing agent that is reactive with theterminal-modified sulfur-containing polymer.

The present disclosure is also directed to methods for makingterminal-modified sulfur-containing polymers and compositions thereof,such as sealant compositions, including aerospace sealant compositions,comprising terminal-modified sulfur-containing polymers provided by thepresent disclosure.

DETAILED DESCRIPTION Definitions

A dash (“-”) that is not between two letters or symbols is used toindicate a point of bonding for a substituent or between two atoms. Forexample, —CONH₂ is bonded to another moiety through the carbon atom.

“Activated ethylenically unsaturated isocyanate” refers to a compoundcomprising an ethylenically unsaturated group and an isocyanate group inwhich the double bond is electron deficient such that it is activatedtoward Michael addition, i.e., the double bond is a Michael acceptor.

“Aldehyde” refers to a compound of the formula CH(O)R where R ishydrogen or a hydrocarbon group such as an alkyl group, as definedherein. In certain embodiments, the aldehyde is C₁₋₁₀ aldehyde, C₁₋₆aldehyde, C₁₋₄ aldehyde, C₁₋₃ aldehyde, and in certain embodiments, C₁₋₂aldehyde. In certain embodiments, the aldehyde is formaldehyde. Incertain embodiments of the aldehyde, R is selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂ cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl.

“Alkanediyl” refers to a diradical of a saturated, branched orstraight-chain, acyclic hydrocarbon group, having, for example, from 1to 18 carbon atoms (C₁₋₁₈), from 1-14 carbon atoms (C₁₋₁₄), from 1-6carbon atoms (C₁₋₆), from 1 to 4 carbon atoms (C₁₋₄), or from 1 to 3hydrocarbon atoms (C₁₋₃). In certain embodiments, the alkanediyl isC₂₋₁₄ alkanediyl, C₂₋₁₀ alkanediyl, C₂₋₈ alkanediyl, C₂₋₆ alkanediyl,C₂₋₄ alkanediyl, and in certain embodiments, C₂₋₃ alkanediyl. Examplesof alkanediyl groups include methane-diyl (—CH₂—), ethane-1,2-diyl(—CH₂CH₂—), propane-1,3-diyl and iso-propane-1,2-diyl (e.g., —CH₂CH₂CH₂—and —CH(CH₃)CH₂—), butane-1,4-diyl (—CH₂CH₂CH₂CH₂—), pentane-1,5-diyl(—CH₂CH₂CH₂CH₂CH₂—), hexane-1,6-diyl (—CH₂CH₂CH₂CH₂CH₂CH₂—),heptane-1,7-diyl, octane-1,8-diyl, nonane-1,9-diyl, decane-1,10-diyl,dodecane-1,12-diyl, and the like.

“Alkanedithiol” refers to an alkane group in which two of the hydrogenatoms are replaced with a thiol group, —SH. In certain embodiments, thealkanedithiol is C₂₋₁₂ alkanedithiol, C₂₋₁₀ alkanedithiol, C₂₋₈alkanedithiol, C₂₋₆ alkanedithiol, and in certain embodiments, C₂₋₃alkanedithiol.

“Alkanearene” refers to a hydrocarbon group having one or more aryland/or arenediyl groups and one or more alkyl and/or alkanediyl groups,where aryl, arenediyl, alkyl, and alkanediyl are defined here. Incertain embodiments, each aryl and/or arenediyl group(s) is C₆₋₁₂,C₆₋₁₀, and in certain embodiments, phenyl or benzenediyl. In certainembodiments, each alkyl and/or alkanediyl group(s) is C₁₋₆, C₁₋₄, C₁₋₃,and in certain embodiments, methyl, methanediyl, ethyl, orethane-1,2-diyl. In certain embodiments, the alkanearene group is C₄₋₁₈alkanearene, C₄₋₁₆ alkanearene, C₄₋₁₂ alkanearene, C₄₋₈ alkanearene,C₆₋₁₂ alkanearene, C₆₋₁₀ alkanearene, and in certain embodiments, C₆₋₉alkanearene. Examples of alkanearene groups include diphenyl methane.

“Alkanearenediyl” refers to a diradical of an alkanearene group. Incertain embodiments, the alkanearenediyl group is C₄₋₁₈ alkanearenediyl,C₄₋₁₆ alkanearenediyl, C₄₋₁₂ alkanearenediyl, C₄₋₈ alkanearenediyl,C₆₋₁₂ alkanearenediyl, C₆₋₁₀ alkanearenediyl, and in certainembodiments, C₆₋₉ alkanearenediyl. Examples of alkanearenediyl groupsinclude diphenyl methane-4,4′-diyl.

“Alkanecycloalkane” refers to a saturated hydrocarbon group having oneor more cycloalkyl and/or cycloalkanediyl groups and one or more alkyland/or alkanediyl groups, where cycloalkyl, cycloalkanediyl, alkyl, andalkanediyl are defined herein. In certain embodiments, each cycloalkyland/or cycloalkanediyl group(s) is C₃₋₆, C₅₋₆, and in certainembodiments, cyclohexyl or cyclohexanediyl. In certain embodiments, eachalkyl and/or alkanediyl group(s) is C₁₋₆, C₁₋₄, C₁₋₃, and in certainembodiments, methyl, methanediyl, ethyl, or ethane-1,2-diyl. In certainembodiments, the alkanecycloalkane group is C₄₋₁₈ alkanecycloalkane,C₄₋₁₆ alkanecycloalkane, C₄₋₁₂ alkanecycloalkane, C₄₋₈alkanecycloalkane, C₆₋₁₂ alkanecycloalkane, C₆₋₁₀ alkanecycloalkane, andin certain embodiments, C₆₋₉ alkanecycloalkane. Examples ofalkanecycloalkane groups include 1,1,3,3-tetramethylcyclohexane andcyclohexylmethane.

“Alkanecycloalkanediyl” refers to a diradical of an alkanecycloalkanegroup. In certain embodiments, the alkanecycloalkanediyl group is C₄₋₁₈alkanecycloalkanediyl, C₄₋₁₆ alkanecycloalkanediyl, C₄₋₁₂alkanecycloalkanediyl, C₄₋₈ alkanecycloalkanediyl, C₆₋₁₂alkanecycloalkanediyl, C₆₋₁₀ alkanecycloalkanediyl, and in certainembodiments, C₆₋₉ alkanecycloalkanediyl. Examples ofalkanecycloalkanediyl groups include1,1,3,3-tetramethylcyclohexane-1,5-diyl and cyclohexylmethane-4,4′-diyl.

“Alkoxy” refers to an —OR group where R is alkyl as defined herein.Examples of alkoxy groups include methoxy, ethoxy, n-propoxy,isopropoxy, and n-butoxy. In certain embodiments, the alkoxy group isC₁₋₈ alkoxy, C₁₋₆ alkoxy, C₁₋₄ alkoxy, and in certain embodiments, C₁₋₃alkoxy.

“Alkyl” refers to a monoradical of a saturated, branched orstraight-chain, acyclic hydrocarbon group having, for example, from 1 to20 carbon atoms, from 1 to 10 carbon atoms, from 1 to 6 carbon atoms,from 1 to 4 carbon atoms, or from 1 to 3 carbon atoms. In certainembodiments, the alkyl group is C₂₋₆ alkyl, C₂₋₄ alkyl, and in certainembodiments, C₂₋₃ alkyl. Examples of alkyl groups include methyl, ethyl,n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-hexyl, n-decyl,tetradecyl, and the like. In certain embodiments, the alkyl group isC₂₋₆ alkyl, C₂₋₄ alkyl, and in certain embodiments, C₂₋₃ alkyl.

“Aminoalkyl” refers to an alkyl group as defined herein, in which one ofthe hydrogen atoms of the alkyl group is replaced with an amino group,—NH₂. In certain embodiments, the aminoalkyl group is C₁₋₁₀ aminoalkyl,C₁₋₆ aminoalkyl, C₁₋₄ aminoalkyl, C₁₋₃ aminoalkyl, and in certainembodiments, C₁₋₂ aminoalkyl.

“Arenediyl” refers to diradical monocyclic or polycyclic aromatic group.Examples of arenediyl groups include benzene-diyl and naphthalene-diyl.In certain embodiments, the arenediyl group is C₆₋₁₂ arenediyl, C₆₋₁₀arenediyl, C₆₋₉ arenediyl, and in certain embodiments, benzene-diyl.

“Aryl” refers to a monovalent aromatic hydrocarbon radical derived bythe removal of one hydrogen atom from a single carbon atom of a parentaromatic ring system. Aryl encompasses 5- and 6-membered carbocyclicaromatic rings, for example, benzene; bicyclic ring systems wherein atleast one ring is carbocyclic and aromatic, for example, naphthalene,indane, and tetralin; and tricyclic ring systems wherein at least onering is carbocyclic and aromatic, for example, fluorene. Arylencompasses multiple ring systems having at least one carbocyclicaromatic ring fused to at least one carbocyclic aromatic ring,cycloalkyl ring, or heterocycloalkyl ring. For example, aryl includes 5-and 6-membered carbocyclic aromatic rings fused to a 5- to 7-memberedheterocycloalkyl ring containing one or more heteroatoms chosen from N,O, and S. For such fused, bicyclic ring systems wherein only one of therings is a carbocyclic aromatic ring, the point of attachment may be atthe carbocyclic aromatic ring or the heterocycloalkyl ring. Examples ofaryl groups include, but are not limited to, groups derived fromaceanthrylene, acenaphthylene, acephenanthrylene, anthracene, azulene,benzene, chrysene, coronene, fluoranthene, fluorene, hexacene,hexaphene, hexylene, as-indacene, s-indacene, indane, indene,naphthalene, octacene, octaphene, octalene, ovalene, penta-2,4-diene,pentacene, pentalene, pentaphene, perylene, phenalene, phenanthrene,picene, pleiadene, pyrene, pyranthrene, rubicene, triphenylene,trinaphthalene, and the like. In certain embodiments, the aryl group canhave from 6 to 20 carbon atoms, and in certain embodiments, from 6 to 12carbon atoms. Aryl, however, does not encompass or overlap in any waywith heteroaryl, separately defined herein. Hence, a multiple ringsystem in which one or more carbocyclic aromatic rings is fused to aheterocycloalkyl aromatic ring, is heteroaryl, not aryl, as definedherein. In certain embodiments, an aryl group is phenyl.

“Arylalkyl” refers to an alkyl group in which one of the hydrogen atomsis replaced with an aryl group. In certain embodiments of an arylalkylgroup, a hydrogen atom on the terminal carbon atom of an alkyl group isreplaced with an aryl group. In certain embodiments of arylalkyl, thearyl group is a C₆₋₁₂ aryl group, in certain embodiments a C₆₋₁₀ arylgroup, and in certain embodiments, a phenyl or naphthyl group. Incertain embodiments, the alkanediyl portion of an arylalkyl group maybe, for example, C₁₋₁₀ alkanediyl, C₁₋₆ alkanediyl, C₁₋₄ alkanediyl,C₁₋₃ alkanediyl, propane-1,3-diyl, ethane-1,2-diyl, or methane-diyl. Incertain embodiments, the arylalkyl group is C₇₋₁₈ arylalkyl, C₇₋₁₆arylalkyl, C₇₋₁₂ arylalkyl, C₇₋₁₀ arylalkyl, or C₇₋₉ arylalkyl. Forexample, C₇₋₉ arylalkyl can include a C₁₋₃ alkyl group bonded to aphenyl group.

“Cycloalkanediyl” refers to a diradical saturated monocyclic orpolycyclic hydrocarbon group. In certain embodiments, thecycloalkanediyl group is C₃₋₁₂ cycloalkanediyl, C₃₋₈ cycloalkanediyl,C₃₋₆ cycloalkanediyl, and in certain embodiments, C₅₋₆ cycloalkanediyl.Examples of cycloalkanediyl groups include cyclohexane-1,4-diyl,cyclohexane-1,3-diyl, and cyclohexane-1,2-diyl.

“Cycloalkyl” refers to a saturated monocyclic or polycyclic hydrocarbonmonoradical group. In certain embodiments, the cycloalkyl group is C₃₋₁₂cycloalkyl, C₃₋₈ cycloalkyl, C₃₋₆ cycloalkyl, and in certainembodiments, C₅₋₆ cycloalkyl.

“Cycloalkylalkyl” refers to an alkyl group in which one of the hydrogenatoms is replaced with a cycloalkyl group. In certain embodiments of thecycloalkylalkyl group, a hydrogen atom on the terminal carbon atom of analkyl group is replaced with a cycloalkyl group. In certain embodimentsof cycloalkylalkyl, the cycloalkyl group is a C₃₋₆ cycloalkyl group, incertain embodiments a C₅₋₆ cycloalkyl group, and in certain embodiments,a cyclopropyl, a cyclobutyl, a cyclopentyl, or a cyclohexyl group. Incertain embodiments, the alkanediyl portion of a cycloalkylalkyl groupmay be, for example, C₁₋₁₀ alkanediyl, C₁₋₆ alkanediyl, C₁₋₄ alkanediyl,C₁₋₃ alkanediyl, propane-1,3-diyl, ethane-1,2-diyl, or methane-diyl. Incertain embodiments, the cycloalkylalkyl group is C₄₋₁₆ cycloalkylalkyl,C₄₋₁₂ cycloalkylalkyl, C₄₋₁₀ cycloalkylalkyl, C₆₋₁₂ cycloalkylalkyl, orC₆₋₉ cycloalkylalkyl. For example, C₆₋₉ cycloalkylalkyl includes a C₁₋₃alkyl group bonded to a cyclopentyl or a cyclohexyl group.

“Cycloalkylalkanediyl” refers to a diradical of a cycloalkylalkanegroup. In certain embodiments, the cycloalkylalkanediyl group is C₄₋₁₆cycloalkylalkanediyl, C₄₋₁₂ cycloalkylalkanediyl, C₄₋₁₀cycloalkylalkanediyl, C₆₋₁₂ cycloalkylalkanediyl, or C₆₋₉cycloalkylalkanediyl. For example, C₆₋₉ cycloalkylalkanediyl includes aC₁₋₃ alkyl group bonded to a cyclopentyl or a cyclohexyl group.

“Cycloalkylalkane” group refers to a saturated, branched orstraight-chain, acyclic hydrocarbon group in which one of the hydrogenatoms is replaced with a cycloalkane group. In certain embodiments ofthe cycloalkylalkane group, a hydrogen atom on the terminal carbon atomof a linear alkane group is replaced with a cycloalkyl group. In certainembodiments the cycloalkyl group is a C₃₋₆ cycloalkyl group, in certainembodiments a C₅₋₆ cycloalkyl group, and in certain embodiments acyclopropyl, a cyclobutyl, a cyclopentyl, or a cyclohexyl group. Thealkane portion of a cycloalkylalkane group may be, for example, C₁₋₁₀alkane, C₁₋₆ alkane, C₁₋₄ alkane, C₁₋₃ alkane, propane, ethane, ormethane. In certain embodiments, a cycloalkylalkane group is C₄₋₁₆cycloalkylalkane, C₄₋₁₂ cycloalkylalkane, C₄₋₁₀ cycloalkylalkane, C₆₋₁₂cycloalkylalkane, or C₆₋₉ cycloalkylalkane. For example, C₆₋₉cycloalkylalkane includes a C₁₋₃ alkyl group bonded to a cyclopentyl ora cyclohexyl group.

“Group derived from a diisocyanate” refers to a group in which one orboth of the terminal isocyanate groups of a parent diisocyanate form aurethane (—O—C(O)—N(R)—), thiourethane (—S—C(O)—N(R)—), or urea linkage(—N(R)—C(O)—N(R)—). The group derived from a diisocyanate includesgroups derived from aliphatic diisocyanates and groups derived fromaromatic diisocyanates. In certain embodiments, the group derived from adiisocyanate is a group derived from an aliphatic diisocyanate, and incertain embodiments a group derived from a diisocyanate is a groupderived from an aromatic diisocyanate. For example, a compound derivedfrom 2,6-diisocyanatotoluene has the structure:

where each R is a bond to a —O—, —S—, or —NR— group.

Examples of aliphatic diisocyanates include, 1,6-hexamethylenediisocyanate, 1,5-diisocyanato-2-methylpentane,methyl-2,6-diisocyanatohexanoate, bis(isocyanatomethyl)cyclohexane,1,3-bis(isocyanatomethyl)cyclohexane, 2,2,4-trimethylhexane1,6-diisocyanate, 2,4,4-trimethylhexane 1,6-diisocyanate,2,5(6)-bis(isocyanatomethyl)cyclo[2.2.1.]heptane,1,3,3-trimethyl-1-(isocyanatomethyl)-5-isocyanatocyclohexane,1,8-diisocyanato-2,4-dimethyloctane,octahydro-4,7-methano-1H-indenedimethyl diisocyanate, and1,1′-methylenebis(4-isocyanatocyclohexane), and 4,4-methylenedicyclohexyl diisocyanate (H₁₂MDI). Examples of aromatic diisocyanatesinclude 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,2,6-toluene diisocyanate (2,6-TDI), 2,4-toluene diisocyanate (2,4-TDI),a blend of 2,4-TDI and 2,6-TDI, 1,5-diisocyanatonaphthalene, diphenyloxide 4,4′-diisocyanate, 4,4′-methylenediphenyl diisocyanate (4,4-MDI),2,4′-methylenediphenyl diisocyanate (2,4-MDI),2,2′-diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate(MDI), 3,3′-dimethyl-4,4′-biphenylene isocyanate,3,3′-dimethoxy-4,4′-biphenylene diisocyanate,1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methyl benzene, and2,4,6-triisopropyl-m-phenylene diisocyanate.

Examples of aromatic diisocyanates in which the isocyanate groups arenot bonded directly to the aromatic ring include,bis(isocyanatoethyl)benzene, α,α, α′,α′-tetramethylxylene diisocyanate,1,3-bis(1-isocyanato-1-methylethyl)benzene, bis(isocyanatobutyl)benzene,bis(isocyanatomethyl)naphthalene, bis(isocyanatomethyl)diphenyl ether,bis(isocyanatoethyl)phthalate, and 2,5-di(isocyanatomethyl)furan.Aromatic diisocyanates having isocyanate groups bonded directly to thearomatic ring include phenylene diisocyanate, ethylphenylenediisocyanate, isopropylphenylene diisocyanate, dimethylphenylenediisocyanate, diethylphenylene diisocyanate, diisopropylphenylenediisocyanate, naphthalene diisocyanate, methylnaphthalene diisocyanate,biphenyl diisocyanate, 4,4′-diphenylmethane diisocyanate,bis(3-methyl-4-isocyanatophenyl)methane, bis(isocyanatophenyl)ethylene,3,3′-dimethoxy-biphenyl-4,4′-diisocyanate, diphenylether diisocyanate,bis(isocyanatophenylether)ethyleneglycol,bis(isocyanatophenylether)-1,3-propyleneglycol, benzophenonediisocyanate, carbazole diisocyanate, ethylcarbazole diisocyanate,dichlorocarbazole diisocyanate, 4,4′-diphenylmethane diisocyanate,p-phenylene diisocyanate, 2,4-toluene diisocyanate, and 2,6-toluenediisocyanate.

Examples of alicyclic diisocyanates include isophorone diisocyanate,cyclohexane diisocyanate, methylcyclohexane diisocyanate,bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane,bis(isocyanatocyclohexyl)-2,2-propane,bis(isocyanatocyclohexyl)-1,2-ethane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-isocyanatomethyl-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-3-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane,2-isocyanatomethyl-2-(3-isocyanatopropyl)-5-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane,and2-isocyanatomethyl-2-(3-isocyanatopropyl)-6-(2-isocyanatoethyl)-bicyclo[2.2.1]-heptane.

“Group derived from an ethylenically unsaturated monoisocyanate” refersto a group in which the isocyanate group of a parent ethylenicallyunsaturated monoisocyanate forms a urethane, thiourethane or urealinkage and the ethylenically unsaturated group is bonded to anothermoiety or that is not bonded to another moiety. In certain embodiments,a group derived from an ethylenically unsaturated isocyanate refers to agroup in which an isocyanate group of a parent ethylenically unsaturatedmonoisocyanate forms a urethane, thiourethane or urea linkage and theethylenically unsaturated group is not bonded to another moiety. Forexample, a group derived from the ethylenically unsaturatedmonoisocyanate 2-isocyanatoethyl methacrylate can have the structure:

where the carbonyl is bonded to —O—, —S—, or —NR— to form a urethane,thiourethane or urea group, respectively. In certain embodiments, agroup derived from an ethylenically unsaturated isocyanate refers to agroup in which an isocyanate group of a parent ethylenically unsaturatedmonoisocyanate forms a urethane, thiourethane or urea linkage and theethylenically unsaturated group is bonded to another moiety. In suchembodiments, a group derived from the ethylenically unsaturatedmonoisocyanate 2-isocyanatoethyl methacrylate has the structure:

where the carbonyl is bonded to —O—, —S—, or —NR— to form a urethane,thiourethane or urea group, and the former vinyl group is bonded toanother moiety.

“Heteroalkanearene” refers to an alkanearene group in which one or moreof the carbon atoms are replaced with a heteroatom, such as N, O, S, orP. In certain embodiments of heteroalkanearene, a heteroatom is selectedfrom N and O.

“Heteroalkanearenediyl” refers to an alkanearenediyl group in which oneor more of the carbon atoms are replaced with a heteroatom, such as N,O, S, or P. In certain embodiments of heteroalkanearenediyl, theheteroatom is selected from N and O.

“Heteroalkanecycloalkane” refers to an alkanecycloalkane group in whichone or more of the carbon atoms are replaced with a heteroatom, such asN, O, S, or P. In certain embodiments of heteroalkanecycloalkane, theheteroatom is selected from N and O.

“Heteroalkanecycloalkanediyl” refers to an alkanecycloalkanediyl groupin which one or more of the carbon atoms are replaced with a heteroatom,such as N, O, S, or P. In certain embodiments ofheteroalkanecycloalkanediyl, the heteroatom is selected from N and O.

“Heteroalkanediyl” refers to an alkanediyl group in which one or more ofthe carbon atoms are replaced with a heteroatom, such as N, O, S, or P.In certain embodiments of heteroalkanediyl, the heteroatom is selectedfrom N and O.

“Heterocycloalkanediyl” refers to a cycloalkanediyl group in which oneor more of the carbon atoms are replaced with a heteroatom, such as N,O, S, or P. In certain embodiments of heterocycloalkanediyl, theheteroatom is selected from N and O.

“Heteroalkyl” refers to an alkyl group in which one or more of thecarbon atoms are replaced with a heteroatom, such as N, O, S, or P. Incertain embodiments of heteroalkyl, the heteroatom is selected from Nand O.

“Heteroarenediyl” refers to an arenediyl group in which one or more ofthe carbon atoms are replaced with a heteroatom, such as N, O, S, or P.In certain embodiments of heteroarenediyl, the heteroatom is selectedfrom N and O.

“Heteroaryl” refers to a monovalent heteroaromatic radical derived bythe removal of one hydrogen atom from a single atom of a parentheteroaromatic ring system. Heteroaryl encompasses multiple ring systemshaving at least one heteroaromatic ring fused to at least one otherring, which can be aromatic or non-aromatic. Heteroaryl encompasses 5-to 7-membered aromatic, monocyclic rings containing one or more, forexample, from 1 to 4, or in certain embodiments, from 1 to 3,heteroatoms chosen from N, O, S, and P with the remaining ring atomsbeing carbon; and bicyclic heterocycloalkyl rings containing one ormore, for example, from 1 to 4, or in certain embodiments, from 1 to 3,heteroatoms chosen from N, O, S, and P, with the remaining ring atomsbeing carbon and wherein at least one heteroatom is present in anaromatic ring. For example, heteroaryl includes a 5- to 7-memberedheteroaromatic ring fused to a 5- to 7-membered cycloalkyl ring. Forsuch fused, bicyclic heteroaryl ring systems wherein only one of therings contains one or more heteroatoms, the point of attachment may beat the heteroaromatic ring or the cycloalkyl ring. In certainembodiments, where the total number of N, O, S, and P atoms in theheteroaryl group exceeds one, the heteroatoms are not adjacent to oneanother. In certain embodiments, the total number of N, O, S, and Patoms in the heteroaryl group is not more than two. In certainembodiments, the total number of N, O, S, and P atoms in the aromaticheterocycle is not more than one. Heteroaryl does not encompass oroverlap with aryl as defined herein. Examples of heteroaryl groupsinclude, but are not limited to, groups derived from acridine,arsindole, carbazole, α-carboline, chromane, chromene, cinnoline, furan,imidazole, indazole, indole, indoline, indolizine, isobenzofuran,isochromene, isoindole, isoindoline, isoquinoline, isothiazole,isoxazole, naphthyridine, oxadiazole, oxazole, perimidine,phenanthridine, phenanthroline, phenazine, phthalazine, pteridine,purine, pyran, pyrazine, pyrazole, pyridazine, pyridine, pyrimidine,pyrrole, pyrrolizine, quinazoline, quinoline, quinolizine, quinoxaline,tetrazole, thiadiazole, thiazole, thiophene, triazole, xanthene, and thelike. In certain embodiments, a heteroaryl group is C₅₋₂₀ heteroaryl,C₅₋₁₂ heteroaryl, C₅₋₁₀ heteroaryl, and in certain embodiments C₅₋₆heteroaryl. In certain embodiments heteroaryl groups are those derivedfrom thiophene, pyrrole, benzothiophene, benzofuran, indole, pyridine,quinoline, imidazole, oxazole, or pyrazine.

“Ketone” refers to a compound of the formula CO(R)₂, where each R is ahydrocarbon group. In certain embodiments of a ketone, each R isindependently selected from C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl, substitutedC₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl, and substituted C₆₋₁₂cycloalkylalkyl. In certain embodiments of the ketone, each R isindependently selected from methyl, ethyl, and propyl. In certainembodiments, the ketone is selected from propan-2-one, butan-2-one,pentan-2-one, and pentan-3-one.

“Phenylalkyl” refers to an alkyl group in which one of the hydrogenatoms is replaced with a phenyl group. In certain embodiments ofphenylalkyl, one of the hydrogen atoms of the terminal carbon atom of alinear alkyl group is replaced with a phenyl group. In certainembodiments, the phenylalkyl group is C₇₋₁₂ phenylalkyl, C₇₋₁₀phenylalkyl, C₇₋₉ phenylalkyl, and in certain embodiments, benzyl.

“Substituted” refers to a group in which one or more hydrogen atoms areeach independently replaced with the same or different substituent(s).In certain embodiments, the substituent is selected from halogen,—S(O)₂OH, —S(O)₂, —SH, —SR where R is C₁₋₆ alkyl, —COOH, —NO₂, —NR₂where each R is independently selected from hydrogen and C₁₋₃ alkyl,—CN, ═O, C₁₋₆ alkyl, —CF₃, —OH, phenyl, C₂₋₆ heteroalkyl, C₅₋₆heteroaryl, C₁₋₆ alkoxy, and —COR where R is C₁₋₆ alkyl. In certainembodiments, the substituent is chosen from —OH, —NH₂, and C₁₋₃ alkyl.

For purposes of the following description, it is to be understood thatembodiments provided by the present disclosure may assume variousalternative variations and step sequences, except where expresslyspecified to the contrary. Moreover, other than in the examples, orwhere otherwise indicated, all numbers expressing, for example,quantities of ingredients used in the specification and claims are to beunderstood as being modified in all instances by the term “about.”Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that may vary depending upon the desired properties to beobtained. At the very least, and not as an attempt to limit theapplication of the doctrine of equivalents to the scope of the claims,each numerical parameter should at least be construed in light of thenumber of reported significant digits and by applying ordinary roundingtechniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contains certainerrors necessarily resulting from the standard variation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges encompassed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between (andincluding) the recited minimum value of about 1 and the recited maximumvalue of about 10, that is, having a minimum value equal to or greaterthan about 1 and a maximum value of equal to or less than about 10.

Reference is now made to certain embodiments of polymers, compositions,and methods. The disclosed embodiments are not intended to be limitingof the claims. To the contrary, the claims are intended to cover allalternatives, modifications, and equivalents.

Difunctional Sulfur-Containing Polymers

As indicated, certain embodiments provided by the present disclosurerelate to terminal-modified sulfur-containing polymers.Sulfur-containing polymers include polythioethers, polydisulfides, andpolymers containing both thioether and disulfide groups. Polythioethergenerally refers to a polymer containing at least two thioether groups,e.g., two —C—S—C— groups. Polydisulfide refers to a polymer containingat least two disulfide groups, e.g., two —C—S—S—C— groups. In additionto at least two thioether and/or disulfide groups, sulfur-containingpolymers provided by the present disclosure comprise at least twoformal, acetal, and/or ketal groups, e.g., at least two —O—C(R)₂—O—groups, where each R is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl.As used herein, “polymer” refers to oligomers, homopolymers, andcopolymers. Unless stated otherwise, molecular weights are numberaverage molecular weights for polymeric materials indicated as “Mn” asdetermined, for example, by gel permeation chromatography using apolystyrene standard in an art-recognized manner.

In certain embodiments, a difunctional sulfur-containing polymer has thestructure of Formula (I):

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; each R² is independently selected from hydrogen, C₁₋₆ alkyl,C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl,substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl, substituted C₃₋₁₂cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl. Each R¹ may be thesame or may be different, and each R² may be the same or may bedifferent.

In certain embodiments of a sulfur-containing polymer of Formula (I),each R¹ is independently selected from C₂₋₆ alkanediyl, C₂₋₄ alkanediyl,C₂₋₃ alkanediyl, and in certain embodiments, ethane-1,2-diyl. In certainembodiments of a sulfur-containing polymer of Formula (I), each R¹ isethane-1,2-diyl.

In certain embodiments of a sulfur-containing polymer of Formula (I),each R² is independently selected from hydrogen, C₁₋₆ alkyl, C₁₋₄ alkyl,C₁₋₃ alkyl, and in certain embodiments, C₁₋₂ alkyl. In certainembodiments of a sulfur-containing polymer of Formula (I), each R² ismethyl, and in certain embodiments, ethyl. In certain embodiments of asulfur-containing polymer of Formula (I), each R² is hydrogen, and incertain embodiments, each R² is selected from hydrogen, methyl, andethyl.

In certain embodiments of a sulfur-containing polymer of Formula (I),each R¹ is the same and is selected from a C₂₋₃ alkanediyl such asethane-1,2-diyl and propane-1,3-diyl; and each R² is the same and isselected from hydrogen and C₁₋₃ alkyl such as methyl, ethyl, and propyl.In certain embodiments of a sulfur-containing polymer of Formula (I),each R² is hydrogen, and in certain embodiments, each R² is methyl. Incertain embodiments of a sulfur-containing polymer of Formula (I), eachR¹ is ethane-1,2-diyl and each R² is hydrogen. In certain embodiments ofa sulfur-containing polymer of Formula (I), each R¹ is the same and isselected from ethane-1,2-diyl and propane-1,3-diyl; and each R² isindependently selected from hydrogen, methyl, and ethyl.

In certain embodiments of a sulfur-containing polymer of Formula (I), nis an integer selected from 1 to 50, an integer selected from 2 to 40,an integer selected from 4 to 30, and in certain embodiments, n is aninteger selected from 7 to 30.

In certain embodiments of a sulfur-containing polymer of Formula (I),each p is the same and is 1, and in certain embodiments, each p is thesame and is 2.

In certain embodiments, a sulfur-containing polymer of Formula (I)comprises the reaction products of (i) a sulfur-containing diol; and(ii) a reactant selected from an aldehyde, a ketone, and a combinationthereof. In certain embodiments of the reaction, the sulfur-containingdiol comprises the structure:

where p is selected from 1 and 2; and each R¹ is independently selectedfrom C₂₋₆ alkanediyl. In certain embodiments of a sulfur-containingdiol, p is 1 and in certain embodiments p is 2. In certain embodimentsof a sulfur-containing diol, each R¹ is the same and in certainembodiments, each R¹ is different. In certain embodiments, each R¹ isselected from C₂₋₅ alkanediyl, C₂₋₄ alkanediyl, C₂₋₃ alkanediyl, and incertain embodiments, R¹ is ethane-1,2-diyl. In certain embodiments ofthe reaction, the sulfur-containing diol comprises a sulfur-containingdiol selected from 2,2′-thiodiethanol, 3,3′-thiobis(propan-1-ol),4,4′-thiobis(butan-1-ol), and a combination of any of the foregoing. Incertain embodiments of the reaction, the sulfur-containing diolcomprises 2,2′-thiodiethanol.

In certain embodiments of the reaction, the sulfur-containing diolcomprises a single type of sulfur-containing diol, and in certainembodiments, comprises a mixture of sulfur-containing diols. A mixtureof sulfur-containing diols may comprise from 5 mol % to 95 mol % of oneor more thioethers (p is 1) and from 95 mol % to 5 mol % of one or moredisulfides (p is 2). In certain embodiments, a mixture ofsulfur-containing diols comprises 50 mol % of one or more thioethers and50 mol % of one or more disulfides. In certain embodiments, a mixture ofsulfur-containing diols comprises from 0 mol % to 30 mol % of one ormore disulfides, and from 100 mol % to 70 mol % of one or morethioethers.

In certain embodiments of the reaction, reactant (ii) is an aldehyde. Incertain embodiments in which reactant (ii) is an aldehyde, the aldehydecomprises a C₁₋₆ aldehyde, a C₁₋₄ aldehyde, a C₁₋₃ aldehyde, and incertain embodiments, a C₁₋₂ aldehyde. In certain embodiments, thealdehyde is formaldehyde.

In certain embodiments of the reaction, reactant (ii) is a ketone. Incertain embodiments in which reactant (ii) is a ketone, the ketone hasthe formula COR₂ where each R² is independently selected from C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl.In certain embodiments of a ketone, each R² is independently selectedfrom methyl, ethyl, and propyl. In certain embodiments, a ketone isselected from propan-2-one, butan-2-one, pentan-2-one, and pentan-3-one.

In certain embodiments, a sulfur-containing polymer of Formula (I) isthe reaction products of reactants comprising 2,2′-thiodiethanol andformaldehyde, and is referred to herein as thiodiglycol polythioether orthiodiglycol polyformal.

The reaction used to prepare a sulfur-containing polymer of Formula (I)may take place in the presence of an acidic catalyst, such as sulfuricacid, sulfonic acid, or a combination thereof. In certain embodiments, asulfonic acid may be used. Examples of sulfonic acids include alkylsulfonic acids such as methane sulfonic acid, ethane sulfonic acidtert-butane sulfonic acid, 2-propane sulfonic acid, and cyclohexylsulfonic acid; alkene sulfonic acids such as α-olefin sulfonic acid,dimerized α-olefin sulfonic acid, and 2-hexene sulfonic acid; aromaticsulfonic acids such as para-toluene sulfonic acids, benzene sulfonicacid, and naphthalene sulfonic acid; and polymer-supported sulfonicacids such as AMBERLYST™ sulfonic acid catalysts available from DowChemical.

In certain embodiments, sulfur-containing polymers of Formula (I) have ahydroxyl number from 10 to 100, from 20 to 80, from 20 to 60, from 20 to50, and in certain embodiments, from 20 to 40. The hydroxyl number isthe hydroxyl content of the sulfur-containing polymer, and may bedetermined, for example, by acetylating the hydroxyl groups andtitrating the resultant acid against potassium hydroxide. The hydroxylnumber is the weight of potassium hydroxide in milligrams that willneutralize the acid from one gram of the sulfur-containing polymer.

In certain embodiments, a sulfur-containing polymer of Formula (I) has anumber average molecular weight from 200 to 6,000 Daltons, from 500 to5,000 Daltons, from 1,000 to 5,000 Daltons, from 1,500 to 4,000 Daltons,and in certain embodiments, from 2,000 to 3,600 Daltons.

Terminal-Modified Difunctional Sulfur-Containing Polymers

In certain embodiments, a terminal-modified sulfur-containing polymercomprises the reaction products of reactants comprising: (a) asulfur-containing polymer of Formula (I):

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂ cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and (b) a compound comprising a terminal group selected from a vinylgroup, a silyl group, and an epoxy group; and a group that is reactivewith the terminal hydroxyl groups of the polymer of Formula (I).

In certain embodiments of a terminal-modified sulfur-containing polymer,the terminal group is a vinyl group and the compound comprising aterminal vinyl group is selected from an ethylenically unsaturatedisocyanate and an ethylenically unsaturated alcohol.

An ethylenically unsaturated isocyanate includes ethylenicallyunsaturated monoisocyanate and ethylenically unsaturated diisocyanatessuch as ethylenically unsaturated aromatic monoisocyanates,ethylenically unsaturated aliphatic monoisocyanates, ethylenicallyunsaturated aromatic diisocyanates, and ethylenically unsaturatedaliphatic diisocyanates.

Examples of ethylenically unsaturated diisocyanates include butenediisocyanate and 1,3-butadiene-1,4-diisocyanate.

Examples of ethylenically unsaturated monoisocyanates include vinylisocyanate, allyl isocyanate, 3-isocyanato-2-methyl-2-propene,methacryloyl isocyanate, isocyanatoethyl methacrylate, vinyl-benzylisocyanate, 3-isocyanato-1-butene, 3-isocyanato-3-methyl-1-butene,4-isocyanato-2-methyl-1-butene, 4-isocyanato-3,3-dimethyl-1-butene,4-isocyanato-4-methyl-1-pentene, and 5-isocyanato-1-pentene,2-isocyanatoethyl methacrylate, and dimethyl-meta-isopropenylbenzylisocyanate (TMI). In certain embodiments, an ethylenically unsaturatedmonoisocyanate is selected from vinyl isocyanate, allyl isocyanate, andmethyacryloyl isocyanate. In certain embodiments, an ethylenicallyunsaturated aliphatic isocyanate is C₂₋₁₀ alkenyl isocyanate, C₂₋₈alkenyl isocyanate, C₂₋₆ alkenyl isocyanate, and in certain embodiments,C₂₋₃ alkenyl isocyanate.

Examples of ethylenically unsaturated alcohols include, for example,allyl alcohol, 3-buten-1-ol, 3-buten-2-ol, ethylene glycol monovinylether, ethylene glycol monoallyl ether, diethylene glycol monoallylether, glycerin monoallyl ether, trimethylolethane monoallyl ether,trimethylolpropane monoallyl ether, polyethylene glycol monoallyl ether,polypropylene glycol monoallyl ether, 1-vinylcyclobutanol,2-vinylcyclobutanol, 3-vinylcyclobutanol, vinylphenol, 2-allyl phenol,4-allylphenol, 4-allyl-2-methoxyphenol, 4-allyl-2,6-dimethoxyphenol,4-(2-propenyl)-1,2-benzenediol, and4-(2,4-dihydroxyphenyl)-3-buten-2-one. In certain embodiments, anethylenically unsaturated alcohol is selected from allyl alcohol,ethylene glycol monoallyl ether, 2-allylphenol, and 4-allylphenol.

In certain embodiments, the compound comprising a vinyl group is anethylenically unsaturated isocyanate and is selected from3-isopropenyl-α,α-dimethylbenzyl isocyanate (CAS 2094-99-7) and2-isocyanatoethyl methacrylate.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the terminal group is a silyl group and thecompound comprising a terminal silyl group is anisocyanatoalkylalkoxysilane. Examples of suitableisocyanatoalkylalkoxysilanes include, for example,isocyanatopropylmethoxysilane, isocyanatopropylmethyldimethoxysilane,isocyanatopropylmethyldiethoxysilane, isocyanatopropyltriethoxysilane,isocyanatopropyltriisopropoxysilane,isocyanatopropylmethyldiisopropoxysilane,isocyanatoneohexyltrimethoxysilane, isocyanatoneohexyldimethoxysilane,isocyanatoneohexyldiethoxysilane, isocyanatoneohexyltriethoxysilane,isocyanatoneohexyltriisopropoxysilane,isocyanatoneohexyldiisopropoxysilane, isocyanatoisoamyltrimethoxysilane,isocyanatoisoamyldimethoxysilane, isocyanatoisoamylmethylsilane,isocyanatoisoamylmethyldiethoxysilane, isocyanatoisoamyltriethoxysilane,isocyanatoisoamyltriisopropoxysilane, andisocyanatoisoamylmethyldiisopropoxysilane. In certain embodiments, theisocyanatoalkyltrialkoxysilane is 3-isocyanatopropyltrimethoxysilane.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the terminal group is an epoxy group and thecompound comprising a terminal epoxy group is selected from C₁₋₆ epoxyalkanol, C₁₋₆ epoxy haloalkane, and a combination thereof. Examples ofsuitable C₁₋₆ alkanol epoxides include oxirane-2-ol,oxirane-2-ylmethanol, and 2-(oxirane-2-yl)ethanol. Examples of suitableC₁₋₆ epoxy haloalkanes include, for example, 2-(chloromethyl)oxirane and2-(2-chloroethyl)oxirane.

In certain embodiments, a terminal-modified sulfur-containing polymercomprises the reaction products of reactants comprising: (a) and (b),wherein (a) comprises the reaction products of reactants comprising (i)and (ii), wherein (i) comprises a sulfur-containing polymer of Formula(I), wherein n is an integer selected from 1 to 50; each p isindependently selected from 1 and 2; each R¹ is independently selectedfrom C₂₋₆ alkanediyl; and each R² is independently selected fromhydrogen, C₁₋₆ alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl,C₆₋₁₂ cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl, substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂aryl; and (ii) comprises a first compound selected from a diisocyanate,an ethylenically unsaturated isocyanate, and a tosylate; and (b)comprises a second compound comprising a terminal group selected from avinyl group, a silyl group, and an epoxy group; and a group selectedfrom a group that is reactive with an isocyanate group, a group that isreactive with an ethylenically unsaturated group, and a group that isreactive with tosylate.

In certain embodiments, an amine-terminated sulfur-containing polymercomprises the reaction products of reactants comprising (a) and (b),where (a) comprises the reaction products of reactants comprising: (i)and (ii), where (i) comprises a sulfur-containing polymer of Formula(I):

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and (ii) comprises a first compound selected from a diisocyanate, anethylenically unsaturated isocyanate, and a tosylate; and (b) comprisesa second compound comprising a terminal amine group and a group selectedfrom a group that is reactive with an isocyanate group, a group that isreactive with an ethylenically unsaturated group, and a group that isreactive with a tosylate.

Examples of diisocyanates include, for example, 1,3-phenylenediisocyanate, 1,4-phenylene diisocyanate, 2,6-toluene diisocyanate(2,6-TDI), 2,4-toluene diisocyanate (2,4-TDI), a blend of 2,4-TDI and2,6-TDI, 1,5-diisocyanato naphthalene, diphenyl oxide 4,4′-diisocyanate,4,4′-methylenediphenyl diisocyanate (4,4-MDI), 2,4′-methylenediphenyldiisocyanate (2,4-MDI), 2,2′-diisocyanatodiphenylmethane (2,2-MDI),diphenylmethane diisocyanate (MDI), 3,3′-dimethyl-4,4′-biphenyleneisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate,1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methyl benzene,2,4,6-triisopropyl-m-phenylene diisocyanate, and 4,4-methylenedicyclohexyl diisocyanate (H₁₂MDI). Other examples of diisocyanates aredisclosed herein.

In certain embodiments of the reaction to form a terminal-modifiedsulfur-containing polymer, the first compound is 2-isocyanatoethylmethacrylate.

Examples of ethylenically unsaturated isocyanates are disclosed herein.

In certain embodiments, the tosylate is a sulfonyl chloride such asp-toluenesulfonyl chloride.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the second compound comprising a terminalamine group is selected from aniline, an aminoalkyl-substituted aniline,an aminoalkyl, and a sulfur-containing diamine. In certain embodiments,an aminoalkyl-substituted aniline is selected from4-(aminomethyl)aniline and 4-(aminoethyl)aniline. In certain embodimentsan aminoalkyl is selected from ethanamine, propan-1-amine, andbutan-1-amine. Suitable sulfur-containing diamines include, for example,ETHACURE® 300.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the terminal group is an amine group and thecompound comprising a terminal amine group is an alkyl-aminobenzoate.Examples of suitable alkylaminobenzoates include, for example, methyl4-aminobenzoate, ethyl 4-aminobenzoate, methyl 3-aminobenzoate, ethyl3-aminobenzoate, methyl 2-aminobenzoate, and ethyl 3-aminobenzoate. Incertain embodiments, an alkyl-aminobenzoate is ethyl 4-aminobenzoate.

In certain embodiments, a thiol-terminated sulfur-containing polymercomprises the reaction products of reactants comprising: (a) and (b),where (a) comprises the reaction products of reactants comprising (i)and (ii), where (i) comprises a sulfur-containing polymer of Formula(I):

where n is an integer selected from 1 to 50; and each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl,substituted C₃₋₁₂ cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and (ii) comprises a first compound selected from a diisocyanate,thiourea, an ethylenically unsaturated isocyanate, and a tosylate; and(b) comprises a mercaptoalkanol when (ii) comprises a diisocyanate; (b)comprises a metal hydrosulfide when (ii) comprises thiourea; (b)comprises a dithiol when (ii) comprises an ethylenically unsaturatedisocyanate; and (b) comprises a metal hydrosulfide when (ii) comprises atosylate.

Examples of suitable diisocyanates include, for example, those describedherein. Examples of suitable ethylenically unsaturated isocyanatesinclude, for example, those described herein.

In certain embodiments of a reaction to form a terminal-modifiedsulfur-containing polymer, the terminal group is a thiol group and thecompound comprising a terminal thiol group is selected from a dithioland an alkyl(bis)oxydialkanethiol. Examples of suitable dithiols includecompounds of the formula HS—R—SH where R is a C₂₋₆ alkanediyl, havingone or more pendant groups, which can be, for example, hydroxyl groups,C₁₋₆ alkyl groups such as methyl or ethyl groups; C₁₋₆ alkoxy, C₆₋₈cycloalkanediyl, C₆₋₁₀ alkanecycloalkanediyl,—[—(CH₂)_(p)—X—]_(q)—(CH₂)_(r)—, or —[—(CH₂)_(p)—X—]—(CH₂)_(r)— in whichat least one —CH₂— unit is substituted with a methyl group and in whicheach p is independently selected from an integer selected from 2 to 6,each q is independently selected from an integer selected from 1 to 5,and each r is independently selected from an integer selected from 2 to10. Dithiols may include one or more heteroatom substituents in thecarbon backbone, for example, dithiols in which X includes a heteroatomsuch as O, S or other bivalent heteroatom radical, a secondary ortertiary amine group such as —NR′—, where R′ is hydrogen or methyl, oranother substituted trivalent heteroatom. In certain embodiments, X is Oor S, and in certain embodiments, p and r are equal, and in certainembodiments both p and r are 2. In certain embodiments, X is a bond.Examples of suitable dithiols include 1,2-ethanedithiol,1,2-propanedithiol, 1,3-propanedithiol, 1,3-butanedithiol,1,4-butanedithiol, 2,3-butanedithiol, 1,3-pentanedithiol,1,5-pentanedithiol, 1,6-hexanedithiol, 1,3-dimercapto-3-methylbutane,dipentenedimercaptan, ethylcyclohexyldithiol, dimercaptodiethylsulfide,methyl-substituted dimercaptodiethylsulfide, dimethyl-substituteddimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide,dimercaptodioxaoctane, and 1,5-dimercapto-3-oxapentane. A dithiol mayhave one or more pendant groups selected from C₁₋₄ alkyl, C₁₋₄ alkoxy,and hydroxyl. Additional examples of suitable mercaptoalkanols include,for example, C₂₋₆ mercaptoalkanols such as 2-mercaptoethan-1-ol,3-mercaptopropan-1-ol, 4-mercaptobutan-1-ol, 5-mercaptopentan-1-ol, and6-mercaptohexan-1-ol. Examples of suitable dithiols include, forexample, C₂₋₁₀ alkanedithiols such as ethane-1,2-dithiol,propane-1,3-dithiol, butane-1,4-dithiol, pentane-1,5-dithiol, andhexane-1,6-dithiol.

In certain embodiments, a dithiol is an alkyl(bis)oxydialkane.Alkyl(bis)oxydialkane thiols may have the general formulaHS—R—O—R′—O—R—HS, where each R and R′ is an alkanediyl such as, forexample, C₂₋₆ alkanediyl, C₂₋₄ alkanediyl, or C₂ alkanediyl. In certainembodiments, a dithiol is selected from dimercaptodiethylsulfide (DMDS),1,8-dimercapto-3,6-dioxaoctane (DMDO), and 1,5-dimercapto-3-oxapentane.

In certain embodiments, a metal hydrosulfide is sodium hydrosulfide. Incertain embodiments, a tosylate is a sulfonyl chloride such asp-toluenesulfonyl chloride.

In certain embodiments of the above terminal-modified sulfur-containingpolymers, the terminal-modified sulfur-containing polymer has a numberaverage molecular weight from 200 to 6,000 Daltons, from 500 to 5,000Daltons, from 1,000 to 5,000 Daltons, from 1,500 to 4,000 Daltons, andin certain embodiments, from 2,000 to 3,600 Daltons.

Certain terminal-modified sulfur-containing polymers provided by thepresent disclosure have the structure of Formula (II):

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; each R² is independently selected from hydrogen, C₁₋₆ alkyl,C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl,substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl, substituted C₃₋₁₂cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl; and each R³ is—OR^(3′) wherein R^(3′) is selected from a vinyl-terminated group, asilyl-terminated group, an amine-terminated group, an epoxy-terminatedgroup, and a thiol-terminated group.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R¹ is independently selected from C₂₋₆ alkanediyl, C₂₋₄ alkanediyl,C₂₋₃ alkanediyl, and in certain embodiments, ethane-1,2-diyl. In certainembodiments of a polymer of Formula (II), each R¹ is ethane-1,2-diyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R² is independently selected from hydrogen, C₁₋₆ alkyl, C₁₋₄ alkyl,C₁₋₃ alkyl, and in certain embodiments, C₁₋₂ alkyl. In certainembodiments of a polymer of Formula (II), each R² is hydrogen, and incertain embodiments, methyl, and in certain embodiments ethyl.

In certain embodiments of a sulfur-containing polymer of Formula (II),each R¹ is the same and is selected from a C₂₋₃ alkanediyl such asethane-1,2-diyl and propane-1,3-diyl; and each R² is the same and isselected from hydrogen and C₁₋₃ alkyl such as methyl, ethyl, and propyl.In certain embodiments of a sulfur-containing polymer of Formula (II),each R¹ is ethane-1,2-diyl. In certain embodiments of asulfur-containing polymer of Formula (II), each R² is hydrogen. Incertain embodiments of a sulfur-containing polymer of Formula (II), eachR¹ is ethane-1,2-diyl and each R² is hydrogen.

In certain embodiments of a sulfur-containing polymer of Formula (II), nis an integer selected from 1 to 50, an integer selected from 2 to 40,an integer selected from 4 to 30, and in certain embodiments, n is aninteger selected from 7 to 30.

In certain embodiments of a sulfur-containing polymer of Formula (II),each p is the same and is 1, and in certain embodiments, each p is thesame and is 2.

In certain embodiments, a sulfur-containing polymer of Formula (II) hasa number average molecular weight from 200 to 6,000 Daltons, from 500 to5,000 Daltons, from 1,000 to 5,000 Daltons, from 1,500 to 4000 Daltons,and in certain embodiments, from 2,000 to 3,600 Daltons.

In certain embodiments of a polymer of Formula (II), each R³ is thesame.

In certain embodiments of a polymer of Formula (II), each R³ is avinyl-terminated group and is independently selected from a group ofFormula (a), Formula (b), Formula (c), Formula (d), and Formula (e):

where each R⁶ is a moiety derived from an ethylenically unsaturatedmonoisocyanate; each R⁷ is selected from C₂₋₆ alkanediyl and C₂₋₆heteroalkanediyl; each R⁸ is selected from hydrogen, C₁₋₆ alkyl, andphenyl; and each R⁹ is selected from C₂₋₆ alkanediyl, C₂₋₆heteroalkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂ arenediyl, C₆₋₁₂heteroarenediyl, substituted C₆₋₁₂ heteroarenediyl, C₃₋₁₂cycloalkanediyl, substituted C₃₋₁₂ cycloalkanediyl, C₃₋₁₂heterocycloalkanediyl, substituted C₃₋₁₂ heterocycloalkanediyl, C₇₋₁₈alkanearenediyl, substituted C₇₋₁₈heteroalkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments, each R⁶ is derived from an ethylenicallyunsaturated aliphatic monoisocyanate, an ethylenically unsaturatedalicyclic monoisocyanate, and in certain embodiments, an ethylenicallyunsaturated aromatic monoisocyanate.

In certain embodiments of Formula (b) and Formula (d), each R⁷ isselected from C₂₋₄ alkanediyl, C₂₋₃ alkanediyl, and in certainembodiments is selected from ethane-1,2-diyl, propane-1,3-diyl,propane-1,2-diyl, and propane-1,1-diyl. In certain embodiments ofFormula (b) and Formula (d), each R⁷ is selected from ethane-1,2-diyland propane-1,3-diyl.

In certain embodiments of Formula (b), Formula (c), Formula (d), andFormula (e), each R⁸ is selected from hydrogen, methyl, ethyl,isopropyl, and n-propyl.

In certain embodiments of Formula (e), each R⁹ is selected from C₂₋₆alkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂ arenediyl, C₃₋₁₂cycloalkanediyl, substituted C₃₋₁₂ cycloalkanediyl, C₇₋₁₈alkanearenediyl, substituted C₇₋₁₈ alkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl. Incertain embodiments of Formula (e), each R⁹ is the same and is selectedfrom methane-diyl, ethane-1,2-diyl, and propane-1,2-diyl. In certainembodiments of Formula (e), each R⁹ is C₂₋₅ alkanediyl, C₂₋₄ alkanediyl,C₂₋₃ alkanediyl, and in certain embodiments, ethane-1,2-diyl.

In certain embodiments of polymers of Formula (II), each R³ is asilyl-terminated group of Formula (f) and Formula (g):

where each R⁶ is derived from an ethylenically unsaturatedmonoisocyanate; each R¹⁰ is independently selected from C₁₋₆ alkyl, C₁₋₆alkoxy, C₅₋₆ cycloalkyl, C₆₋₁₂ cycloalkylalkyl, phenyl, and C₇₋₁₂phenylalkyl; wherein at least one R¹⁰ is C₁₋₆ alkoxy; and each R¹¹ isC₁₋₆ alkanediyl.

In certain embodiments of Formula (g), each R¹¹ is selected frommethane-diyl, ethane-1,2-diyl, and propane-1,2-diyl. In certainembodiments of Formula (f) and Formula (g), each R¹⁰ is the same and isselected from methoxy, ethoxy, and propoxy. In certain embodiments ofFormula (f) and Formula (g), the silyl-terminal group is atrialkoxysilane, in certain embodiments, a dialkoxysilane, and incertain embodiments, a monoalkoxysilane.

In certain embodiments of a polymer of Formula (II), each R³ is anamine-terminated group and is independently selected from a group ofFormula (h), Formula (i), Formula (j), Formula (k), Formula (l), andFormula (m):

where each R⁶ is selected from a group derived from a diisocyanate and agroup derived from an ethylenically unsaturated monoisocyanate; each R⁷is selected from a bond and C₂₋₆ alkanediyl; each R⁹ is selected fromC₂₋₆ alkanediyl, C₂₋₆ heteroalkanediyl, C₆₋₁₂ arenediyl, substitutedC₆₋₁₂ arenediyl, C₆₋₁₂ heteroarenediyl, substituted C₆₋₁₂heteroarenediyl, C₃₋₁₂ cycloalkanediyl, substituted C₃₋₁₂cycloalkanediyl, C₃₋₁₂ heterocycloalkanediyl, substituted C₃₋₁₂heterocycloalkanediyl, C₇₋₁₈ alkanearenediyl, substitutedC₇₋₁₈heteroalkanearenediyl, C₄₋₁₈ alkanecycloalkanediyl, and substitutedC₄₋₁₈ alkanecycloalkanediyl; and each R¹² is selected from hydrogen,C₁₋₆ alkyl, C₆₋₁₂ aryl, substituted C₆₋₁₂ aryl, C₃₋₁₂ cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₇₋₁₈ arylalkyl, substituted C₇₋₁₈arylalkyl, C₄₋₁₈ alkylcycloalkyl, and substituted C₄₋₁₈ alkylcycloalkyl.

In certain embodiments of Formula (h), each R⁶ is a group derived from adiisocyanate, and in certain embodiments the group is derived from TDI,ISONATE™ 143L (polycarbodiimide-modified diphenylmethane diisocyanate),DESMODUR® N3400 (1,3-diazetidine-2,4-dione,1,3-bis(6-isocyanatohexyl)-), DESMODUR® (I) (isophorone diisocyanate,IPDI), of DESMODUR® W (H₁₂MDI).

In certain embodiments of Formula (h), each R⁶ is a group derived froman ethylenically unsaturated monoisocyanate, and in certain embodimentsis selected from 2-isocyanatoethyl methacrylate.

In certain embodiments of Formula (j), Formula (k), Formula (l), andFormula (m), each R⁷ is selected from C₂₋₄ alkanediyl, C₂₋₃ alkanediyl,and in certain embodiments is selected from ethane-1,2-diyl,propane-1,3-diyl, propane-1,2-diyl, and propane-1,1-diyl. In certainembodiments of Formula (j), Formula (k), Formula (l), and Formula (m),each R⁷ is selected from ethane-1,2-diyl and propane-1,3-diyl.

In certain embodiments of Formula (k) and Formula (l), each R⁹ isselected from C₂₋₆ alkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂arenediyl, C₃₋₁₂ cycloalkanediyl, substituted C₃₋12 cycloalkanediyl,C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈ alkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments of Formula (h), Formula (i), Formula (j), Formula(k), Formula (l), and Formula (m), each R¹² is selected from C₁₋₆ alkyl,phenyl, and amino-substituted phenyl. In certain embodiments of Formula(h), Formula (i), Formula (j), Formula (k), Formula (l), and Formula(m), each R¹² is selected from phenyl, methyl, ethyl, propyl,methyl-phenyl, ethyl-phenyl, propyl-phenyl, benzyl, phenethyl,—(CH₂)-aniline, and aminophenyl.

In certain embodiments of a moiety of Formula (f), R⁷ is —CH(CH₃)—CH₂—.

In certain embodiments of a polymer of Formula (II), each R³ is anepoxy-terminated group and is a group of Formula (n):

where each R¹¹ is independently C₁₋₆ alkanediyl.

In certain embodiments of Formula (n), each R¹¹ is selected frommethanediyl, ethane-1,2-diyl, and propane-1,3-diyl. In certainembodiments, each R¹¹ is the same and is selected from methanediyl,ethane-1,2-diyl, and propane-1,3-diyl.

In certain embodiments of a polymer of Formula (II), each R³ is athiol-terminated group and is independently selected from a group ofFormula (o), Formula (p), Formula (q), Formula (r), Formula (s), Formula(t), Formula (u), and Formula (v):

where each R⁶ is selected from a moiety derived from a diisocyanate anda moiety derived from an ethylenically unsaturated monoisocyanate; eachR⁷ is selected from C₂₋₁₄ alkanediyl and C₂₋₁₄ heteroalkanediyl; andeach R⁹ is selected from C₂₋₆ alkanediyl, C₂₋₆ heteroalkanediyl, C₆₋₁₂arenediyl, substituted C₆₋₁₂ arenediyl, C₆₋₁₂ heteroarenediyl,substituted C₆₋₁₂ heteroarenediyl, C₃₋12 cycloalkanediyl, substitutedC₃₋₁₂ cycloalkanediyl, C₃₋₁₂ heterocycloalkanediyl, substituted C₃₋₁₂heterocycloalkanediyl, C₇₋₁₈ alkanearenediyl, substitutedC₇₋₁₈heteroalkanearenediyl, C₄₋₁₈ alkanecycloalkanediyl, and substitutedC₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments of Formula (o), each R⁶ is a group derived from adiisocyanate, and in certain embodiments the group is derived from TDI,ISONATE™ 143L (polycarbodiimide-modified diphenylmethane diisocyanate),DESMODUR® N3400 (1,3-diazetidine-2,4-dione,1,3-bis(6-isocyanatohexyl)-), DESMODUR® I (isophorone diisocyanate,IPDI), or DESMODUR® W (H₁₂MDI).

In certain embodiments of Formula (o), each R⁶ is a group derived froman ethylenically unsaturated monoisocyanate, and in certain embodimentsis 2-isocyanatoethyl methacrylate.

In certain embodiments of Formula (o), Formula (p), Formula (q), Formula(s), Formula (t), Formula (u), and Formula (v), each R⁷ is selected fromC₂₋₆ alkanediyl. In certain embodiments of Formula (o), Formula (p),Formula (q), Formula (s), Formula (t), Formula (u), and Formula (v),each R⁷ is selected from —CH₂— S—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—,—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—, and —(CH₂)₂—S—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—.

In certain embodiments of Formula (t) and Formula (u), each R⁹ isselected from C₂₋₆ alkanediyl, C₆₋₁₂ arenediyl, substituted C₆₋₁₂arenediyl, C₃₋₁₂ cycloalkanediyl, substituted C₃₋12 cycloalkanediyl,C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈ alkanearenediyl, C₄₋₁₈alkanecycloalkanediyl, and substituted C₄₋₁₈ alkanecycloalkanediyl.

In certain embodiments, an amine-terminated sulfur-containing polymerhas the structure of Formula (III):

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; each R² is independently selected from hydrogen, C₁₋₆ alkyl,C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl,substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl, substituted C₃₋₁₂cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl, and each R⁶ isindependently selected from hydrogen, C₅₋₆ cycloalkyl, phenyl, C₁₋₆alkyl. In certain embodiments of a polymer of Formula (III), each p is1, and in certain embodiments each p is 2. In certain embodiments of apolymer of Formula (III), each R¹ may be the same or may be different.In certain embodiments of a polymer of Formula (III), each R¹ is C₂₋₅alkanediyl, C₂₋₄ alkanediyl, C₂₋₃ alkanediyl, and in certainembodiments, ethane-1,2-diyl. In certain embodiments of a polymer ofFormula (III), each R² may be the same and in certain embodiments may bedifferent. In certain embodiments of a polymer of Formula (III), each R²is hydrogen, C₁₋₅ alkyl, C₁₋₄ alkyl, n-propyl, isopropyl, ethyl, and incertain embodiments, methyl. In certain embodiments of a polymer ofFormula (III), each R¹ is the same and is selected from ethane-1,2-diyl,propane-1,2-diyl and propane-1,3-diyl; and each R² is the same and isselected from hydrogen, methyl, and ethyl. In certain embodiments of apolymer of Formula (III), each R⁶ is the same and is selected fromhydrogen, cyclohexyl, phenyl, methyl, ethyl, and propyl. In certainembodiments of a polymer of Formula (III), n is an integer selected from5 to 40, and in certain embodiments, an integer selected from 10 to 40.

In certain embodiments, a thiol-terminated sulfur-containing polymer isselected from Formula (IVa) and Formula (IVb):

where n is an integer selected from 1 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; each R² is independently selected from hydrogen, C₁₋₆ alkyl,C₇₋₁₂ phenylalkyl, substituted₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl,substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂cycloalkyl, substituted C₃₋₁₂cyclo alkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl; and each R⁶ isindependently selected from C₂₋₆ alkanediyl and C₅₋₁₂ heteroalkanediyl.In certain embodiments of a polymer of Formulae (IVa) and (IVb), each pis 1 and in certain embodiments, each p is 2. In certain embodiments ofa polymer of Formulae (IVa) and (IVb), each R¹ may be the same and incertain embodiments, R¹ may be different. In certain embodiments of apolymer of Formulae (IVa) and (IVb), each R¹ is C₂₋₅ alkanediyl, C₂₋₄alkanediyl, propane-1,3-diyl, propane-1,2-diyl, and in certainembodiments, ethane-1,2-diyl. In certain embodiments of a polymer ofFormulae (IVa) and (IVb), each R¹ is the same and is selected fromethane-1,2-diyl and propane-1,3-diyl, and each R² is the same and isselected from hydrogen, methyl, and ethyl. In certain embodiments of apolymer of Formulae (IVa), each R⁶ is the same and is selected fromethane-1,2-diyl and propane-1,3-diyl. In certain embodiments of apolymer of Formulae (IVa) and (IVb), n is an integer selected from 5 to40, and in certain embodiments, an integer selected from 10 to 40.

Synthesis of Sulfur-Containing Polymers

Difunctional sulfur-containing polymers provided by the presentdisclosure and precursors thereof may be prepared by a number of methodsknown to those skilled in the art, including those described in theexamples herein. For example, to obtain difunctional sulfur-containingpolymers of Formula (I), a sulfur-containing diol and an aldehyde and/orketone may be reacted in an organic solvent in the presence of asulfonic acid catalyst such as AMBERLYST™ 15 to provide thecorresponding difunctional sulfur-containing polymer of Formula (I).

Synthesis of Terminal-Modified Difunctional Sulfur-Containing PolymerDerivatives

Terminal-modified difunctional sulfur-containing polymers provided bythe present disclosure and precursors thereof may be prepared by anumber of methods known to those skilled in the art, including thosedescribed in the Examples herein. For example, to obtainterminal-modified difunctional sulfur-containing polymers of Formula(II), a difunctional sulfur-containing polymer of Formula (I) may bereacted with a compound having appropriate terminal groups.

For example, to obtain a vinyl-terminated sulfur-containing polymer ofFormula (II), a sulfur-containing polymer of Formula (I) may be reactedwith a compound containing a terminal vinyl group and an isocyanategroup such as a group derived from TMI, 2-isocyanatoethyl methacrylate,or allyl isocyanate, in the presence of dibutyltin dilaurate catalyst at76° C. As a further example, a sulfur-containing polymer of Formula (I)may be reacted with an alkene-ol such as 3-butene-1-ol and an aldehydesuch as formaldehyde in the presence of a sulfonic acid (e.g., 4.7 meq/gH⁺) such as AMBERLYST™ 15 in an organic solvent such as toluene toprovide a vinyl-terminated sulfur-containing polymer of Formula (II).

Silyl-terminated sulfur-containing polymers of Formula (II) may beprepared, for example, by reacting a sulfur-containing polymer ofFormula (I) with an isocyanatoalkyltrialkoxysilane such as a3-isocyanatopropyltrimethoxysilane or 3-isocyanatopropyltriethoxysilanein the presence of dibutyltin dilaurate at a temperature of 76° C. toprovide the corresponding silyl-terminated sulfur-containing polymer ofFormula (II).

Epoxy-terminated sulfur-containing polymers of Formula (II) may beprepared, for example, by reacting a sulfur-containing polymer ofFormula (I) in the presence of a monoepoxide such as epichlorohydrin toprovide the corresponding epoxy-terminated sulfur-containing polymer ofFormula (II).

Amine-terminated sulfur-containing polymers of Formula (III) may beprepared, for example, by reacting a vinyl-terminated sulfur-containingpolymer Formula (II)(d) with aniline, an amino-substituted aniline suchas 4-(aminomethyl)aniline, or an alkylamine such as n-butylamineoptionally in the presence of a catalyst such as1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in an organic solvent toprovide the corresponding amine-terminated sulfur-containing polymer ofFormula (III). Alternatively, amine-terminated sulfur-containingpolymers of Formula (III) may be obtained by reacting anisocyanate-terminated sulfur-containing polymer of Formula (I) with adiamine such as 4-(aminomethyl)aniline to provide the correspondingamine-terminated sulfur-containing polymer of Formula (III).Amine-terminated sulfur-containing polymers of Formula (III) may also beobtained by reacting a sulfur-containing polymer of Formula (I) with anamino-substituted benzoate such as ethyl-4-aminobenzoate in the presenceof Bu₂SnO or NaOMe at elevated temperature to provide the correspondingamine-terminated sulfur-containing polymer of Formula (I).Amine-terminated sulfur-containing polymers of Formula (III) may also beprepared by reacting a tosyl-ester of a sulfur-containing polymer ofFormula (III) with an amine-containing compound such as aniline in anorganic solvent at elevated temperature to provide the correspondingamine terminated sulfur-containing polymer of Formula (III).

Thiol-terminated sulfur-containing polymers of Formula (IV) may beprepared by reacting a vinyl-terminated sulfur-containing polymer ofFormula (II) such as the 2-isocyanatoethyl methacrylate adduct or theallyl isocyanate adduct as disclosed herein with a dithiol such as DMDO.Thiol-terminated sulfur-containing polymers of Formula (IV) may also beprepared by reacting a tosyl-ester of a sulfur-containing polymer ofFormula (I) with NaSH in the presence of MeN(Bu)₃ ⁺Cl⁻ in water toprovide the corresponding thiol-terminated sulfur-containing polymer ofFormula (IV). Alternatively, a tosyl-ester of a sulfur-containingpolymer of Formula (I) may be reacted with thiourea in the presence ofMeN(Bu)₃ ⁺Cl⁻ in water to provide the tosylate salt of the thioureaadduct, which may then be reacted in the presence of base at elevatedtemperature to provide the corresponding thiol-terminatedsulfur-containing polymer of Formula (IV). Alternatively, to obtainthiol-terminated sulfur-containing polymers of Formula (IV), asulfur-containing polymer of Formula (I) may first be reacted with adiisocyanate such as TDI in the presence of dibutyltin dilaurate at 75°C. to 80° C. to provide the corresponding isocyanate-terminatedsulfur-containing polymer of Formula (IV). The isocyanate-terminatedsulfur-containing polymer of Formula (IV) may then be reacted with amercaptoalkanol such as 2-mercaptoethanol or 3-mercaptopropanol toprovide the corresponding thiol-terminated sulfur-containing polymer ofFormula (IV).

Isocyanate-terminated sulfur-containing polymers of Formula (II) may beprepared, for example, by reacting a sulfur-containing polymer ofFormula (I) with a diisocyanate such as TDI, ISONATE™ 143L(polycarbodiimide-modified diphenylmethane diisocyanate), DESMODUR®N3400 (1,3-diazetidine-2,4-dione, 1,3-bis(6-isocyanatohexyl)-),DESMODUR® I (isophorone diisocyanate, IPDI), or DESMODUR® W (H₁₂MDI)optionally in the presence of a catalyst such as dibutyltin dilaurate ata temperature from 70° C. to 80° C. Isocyanate-terminatedsulfur-containing polymers may be used as intermediates in the synthesisof other terminal-modified sulfur-containing polymers such as certainamine-terminated and thiol-terminated sulfur-containing polymersprovided by the present disclosure.

Properties of Terminal-Modified Difunctional Sulfur-Containing Polymers

In certain embodiments, terminal-modified difunctional sulfur-containingpolymers provided by the present disclosure are liquid at roomtemperature. Moreover, in certain embodiments, the sulfur-containingpolymers have a viscosity, at 100% solids, of no more than 500 poise,such as 10 to 300 poise or, in some cases, 100 to 200 poise, at atemperature of 25° C. and a pressure of 760 mm Hg determined accordingto ASTM D-2849 §79-90 using a Brookfield CAP 2000 viscometer. In certainembodiments, the T_(g) (glass transition temperature) ofsulfur-containing polymer provided by the present disclosure is nothigher than −40° C., and in certain embodiments, is not higher than −50°C.

Uses

Terminal-modified difunctional sulfur-containing polymers provided bythe present disclosure may be used in compositions, such as sealants,coatings, and/or electrical potting compositions that include one ormore of the sulfur-containing polymers provided by the presentdisclosure. A sealant composition refers to a composition capable ofproducing a film that has the ability to resist operational conditions,such as moisture and temperature, and at least partially block thetransmission of materials, such as water, fuel, and other liquid andgases. In certain embodiments, sealant compositions provided by thepresent disclosure are useful, e.g., as aerospace sealants and aslinings for fuel tanks.

In certain embodiments, compositions provided by the present disclosurecomprise, in addition to a sulfur-containing polymer of Formula (II),Formula (III), Formula (IVa), Formula (IVb), or a reaction product ofany one of the reactions disclosed herein, or a combination of any ofthe foregoing, one or more additional sulfur-containing polymers. Asulfur-containing polymer can be any polymer having at least one sulfuratom in the repeating unit, including polymeric thiols, polythiols,thioethers, polythioethers, polyformals, and polysulfides. A “thiol,” asused herein, refers to a compound comprising a thiol or mercaptan group,that is, an “SH” group, either as the sole functional group or incombination with other functional groups, such as hydroxyl groups, as isthe case with, for example, thioglycerols. A polythiol refers to such acompound having more than one SH group, such as a dithiol or higherfunctionality thiol. Such groups are typically terminal and/or pendantsuch that they have an active hydrogen that is reactive with otherfunctional groups. As used herein, the term “polysulfide” refers to anycompound that comprises a sulfur-sulfur linkage (—S—S—). A polythiol cancomprise both a terminal and/or pendant sulfur (—SH) and a non-reactivesulfur atom (—S— or —S—S—). Thus, the term polythiol generallyencompasses polythioethers and polysulfides. Examples of additionalsulfur-containing polymers suitable in compositions provided by thepresent disclosure include, for example, those disclosed in U.S. Pat.Nos. 6,172,179, 6,509,418, and 7,009,032. In certain embodiments,compositions provided by the present disclosure comprise a polythioetherhaving the structure:—R¹—[—S—(CH₂)₂—O—[—R²—O—]_(m)—(CH₂)₂—S—R¹—]_(n)—wherein R¹ is selected from a C₂₋₆ alkanediyl, C₆₋₈ cycloalkanediyl,C₆₋₁₀ cycloalkylalkanediyl, —[(—CH₂—)_(p)—X—]_(q)—(—CH₂—)_(r)—, and—[(—CH₂—)_(p)—X—]_(q)—(—CH₂—)_(r)— in which at least one —CH₂— unit issubstituted with a methyl group; R² is selected from C₂₋₆ alkanediyl,C₆₋₈ cycloalkanediyl, C₆₋₁₀ cycloalkylalkanediyl, and—[(—CH₂—)_(p)—X—]_(q)—(—CH₂—)_(r)—; X is selected from O, S, and —NR⁶—,where R⁶ is selected from hydrogen and methyl; m is an integer selectedfrom 0 to 10; n is an integer selected from 1 to 60; p is an integerselected from 2 to 6; q is an integer selected from 1 to 5, and r is aninteger selected from 2 to 10. Such polythioethers are described in U.S.Pat. No. 6,172,179 at col. 2, line 29 to col. 4, line 34. The one ormore additional sulfur-containing polymers may be difunctional ormultifunctional, for example, having from 3 to 6 terminal groups, or amixture thereof.

In certain embodiments, compositions provided by the present disclosurecomprise from 10 wt % to 90 wt % of a sulfur-containing polymer providedby the present disclosure, from 20 wt % to 80 wt %, from 30 wt % to 70wt %, and in certain embodiments from 40 wt % to 60 wt %, where wt % isbased on the total weight of all non-volatile components of thecomposition (i.e., the dry weight). In certain embodiments, compositionsprovided by the present disclosure comprise from 10 wt % to 90 wt % of asulfur-containing polymer provided by the present disclosure, from 20 wt% to 90 wt %, from 30 wt % to 90 wt %, from 40 wt % to 90 wt %, from 50wt % to 90 wt %, from 60 wt % to 90 wt %, from 70 wt % to 90 wt %, andin certain embodiments from 80 wt % to 90 wt %, where wt % is based onthe total weight of all non-volatile components of the composition(i.e., the dry weight).

Curing agents suitable in compositions provided by the presentdisclosure include compounds that are reactive with the terminal groupsof the sulfur-containing polymer, such as compounds that are reactivewith hydroxyl groups, vinyl groups, epoxy groups, thiol groups aminegroups, or isocyanate groups.

Examples of suitable curing agents that are reactive with hydroxylgroups include diisocyanates and polyisocyanates, examples of which aredisclosed herein.

Examples of suitable curing agents that are reactive with vinyl groupsinclude dithiols and polythiols, examples of which are disclosed herein.

Silyl-terminated sulfur-containing polymers provided by the presentdisclosure hydrolyze in the presence of water inducing selfpolymerization via condensation. Other catalysts for use withsilyl-terminated sulfur-containing polymers include organotitaniumcompounds such as tetraisopropoxy titanium, tetra-tert-butoxy titanium,titanium di(isopropoxy)bis(ethylacetoacetate), and titaniumdi(isopropoxy)bis(acetylacetoacetate); organic tin compounds dibutyltindilaurate, dibutyltin bisacetylacetoacetate, and tin octylate; metaldicarboxylates such as lead dioctylate; organozirconium compounds suchas zirconium tetraacetyl acetonate; and organoaluminium compounds suchas aluminum triacetyl-acetonate. Specific examples include diisopropoxybis(ethyl acetoacetonate)titanium, diisopropoxy bis(acetylacetonate)titanium, and dibutoxy bis(methyl acetoacetonate)titanium. Itcan be appreciated that because the curing agent for silyl-terminatedsulfur-containing polymers can be atmospheric moisture, it is notnecessary to include a curing agent to a curable composition containingsilyl-terminated sulfur-containing polymers. Therefore, compositionscomprising silyl-terminated sulfur-containing polymers and a curingagent for the silyl group refer to atmospheric moisture.

Examples of suitable curing agents that are reactive with epoxy groupsinclude amines such as diethylenetriamine (DTA), triethylenetetramine(TTA), tetraethylenepentamine (TEPA), dipropenediamine (DPDA),diethylaminopropylamine (DEAPA), N-aminoethylpiperazine (N-AEP),isophoronediamine (IPDA), m-xylenediamine, diaminodiphenylmethane (DDM),diaminodiphenylsulfone (DDS); aromatic amines, ketimine; polyamines;polyamides; phenolic resins; anhydrides such phthalic anhydride,trimellitic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bistrimellitate, glyceroltristrimellitate, maleic anhydride, tetrahydrophthalic anhydride,methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalicanhydride; polymercaptans; polysulfides; ultraviolet curing agents suchas diphenyliodinium hexafluorophosphate, triphenylsulfoniumhexafluorophosphate; and other curing agents known to those skilled inthe art.

Examples of suitable curing agents that are reactive with thiol groupsinclude diepoxides.

Examples of suitable curing agents that are reactive with amine groupsinclude polymeric polyisocyanates, non-limiting examples of whichinclude polyisocyanates having backbone groups chosen from urethanegroups (—NH—C(O)—O—), thiourethane groups (—NH—C(O)—S—), thiocarbamategroups (—NH—C(S)—O—), dithiourethane linkages (—NH—C(S)—S—), andcombinations of any of the foregoing.

Examples of suitable curing agents that are reactive with isocyanategroups include diamines, polyamines, polythiols, and polyols, includingthose disclosed herein.

Compositions provided by the present disclosure may contain from 90% to150%, from 95% to 125%, and in certain embodiments, from 95% to 105% ofthe stoichiometric amount, where the stoichiometric amount is theproportion of the number of reactive isocyanate groups to the number ofgroups reactive with the isocyanate groups. For example, a compositioncontaining the same number of isocyanate groups and amine groups priorto reaction will have a stoichiometric amount of isocyanate groups andamine groups.

Compositions provided by the present disclosure may contain one or moredifferent types of filler. Suitable fillers include those commonly knownin the art, including inorganic fillers, such as carbon black andcalcium carbonate (CaCO₃), and lightweight fillers. Suitable lightweightfillers include, for example, those described in U.S. Pat. No.6,525,168. In certain embodiments, a composition includes 5 wt % to 60wt % of the filler or combination of fillers, 10 wt % to 50 wt %, and incertain embodiments, from 20 wt % to 40 wt %, based on the total dryweight of the composition.

As can be appreciated, the sulfur-containing polymers, curing agents,and fillers employed in a composition, as well as any additives, may beselected so as to be compatible with each other.

Compositions provided by the present disclosure may include one or morecolorants, thixotropic agents, accelerators, retardants, adhesionpromoters, solvents, masking agents, or a combination of any of theforegoing.

As used herein, the term “colorant” means any substance that impartscolor and/or other opacity and/or other visual effect to thecomposition. A colorant can be of any suitable form, such as discreteparticles, dispersions, solutions, and/or flakes. A single colorant or amixture of two or more colorants can be used in a composition.

Examples of colorants include pigments, dyes and tints, such as thoseused in the paint industry and/or listed in the Dry Color ManufacturersAssociation (DCMA), as well as special effect compositions. A colorantmay include, for example, a finely divided solid powder that isinsoluble but wettable under the conditions of use. A colorant may beorganic or inorganic and may be agglomerated or non-agglomerated.Colorants may be incorporated into a composition by use of a grindvehicle, such as an acrylic grind vehicle.

Examples of pigments and/or pigment compositions include carbazoledioxazine crude pigment, azo, monoazo, diazo, naphthol AS, salt type(flakes), benzimidazolone, isoindolinone, isoindoline, polycyclicphthalocyanine, quinacridone, perylene, perinone, diketopyrrolo pyrrole,thioindigo, anthraquinone, indanthrone, anthrapyrimidine, flavanthrone,pyranthrone, anthanthrone, dioxazine, triarylcarbonium, quinophthalonepigments, diketo pyrrolo pyrrole red (DPPBO red), titanium dioxide,carbon black, and combinations of any of the foregoing.

Examples of dyes include, but are not limited to, those that aresolvent- and/or aqueous-based such as phthalo green or blue, iron oxide,bismuth vanadate, anthraquinone, perylene, and quinacridone.

Examples of tints include pigments dispersed in water-based orwater-miscible carriers such as AQUA-CHEM 896 commercially availablefrom Degussa, Inc., CHARISMA COLORANTS and MAXITONER INDUSTRIALCOLORANTS commercially available from Accurate Dispersions division ofEastman Chemical, Inc.

As noted above, a colorant may be in the form of a dispersion including,for example, a nanoparticle dispersion. Nanoparticle dispersions mayinclude one or more highly dispersed nanoparticle colorants and/orcolorant particles that produce a desired visible color and/or opacityand/or visual effect. Nanoparticle dispersions may include colorantssuch as pigments or dyes having a particle size of less than 150 nm,such as less than 70 nm, or less than 30 nm. Nanoparticles may beproduced by milling stock organic or inorganic pigments with grindingmedia having a particle size of less than 0.5 mm. Examples ofnanoparticle dispersions and methods for making them are disclosed inU.S. Pat. No. 6,875,800. Nanoparticle dispersions may also be producedby crystallization, precipitation, gas phase condensation, and/orchemical attrition (i.e., partial dissolution). To minimizere-agglomeration of nanoparticles within the coating, a dispersion ofresin-coated nanoparticles may be used. As used herein, a “dispersion ofresin-coated nanoparticles” refers to a continuous phase in which aredispersed discreet “composite microparticles” that comprise ananoparticle and a resin coating on the nanoparticle. Examples ofdispersions containing resin-coated nanoparticles and methods for makingthem are disclosed in U.S. Pat. No. 7,438,972.

Examples of special effect compositions that may be used in compositionsprovided by the present disclosure include pigments and/or compositionsthat produce one or more appearance effects such as reflectance,pearlescence, metallic sheen, phosphorescence, fluorescence,photochromism, photosensitivity, thermochromism, goniochromism, and/orcolor-change. Additional special effect compositions can provide otherperceivable properties, such as opacity or texture. In certainembodiments, special effect compositions may produce a color shift, suchthat the color of a composition changes when the coating is viewed atdifferent angles. Examples of color effect compositions are disclosed inU.S. Pat. No. 6,894,086. Additional color effect compositions mayinclude transparent coated mica and/or synthetic mica, coated silica,coated alumina, a transparent liquid crystal pigment, a liquid crystalcoating, and/or any composition wherein interference results from arefractive index differential within the material and not because of therefractive index differential between the surface of the material andthe air.

In general, a colorant may comprise from 1 wt % to 65 wt % of acomposition, from 2 wt % to 50 wt %, such as from 3 wt % to 40 wt %, orfrom 5 wt % to 35 wt %, with weight percent based on the total dryweight of the composition.

Thixotropes, for example, silica, may be used in an amount from 0.1 wt %to 5 wt %, based on the total dry weight of the composition.

Cure catalysts known to the art, such as amines, may be present in anamount from 0.1 to 5 weight percent, based on the total weight of thecomposition. Examples of suitable catalysts include1,4-diaza-bicyclo[2.2.2]octane (DABCO®, commercially available from AirProducts, Chemical Additives Division, Allentown, Pa.) and DMP-30® (anaccelerant composition including 2,4,6-tris(dimethylaminomethyl)phenol.

Retardants, such as stearic acid, may be used in an amount from 0.1 wt %to 5 wt % of a composition, based on the total dry weight of thecomposition. Adhesion promoters, may be present in amount from 0.1 wt %to 15 wt % of a composition, based on the total dry weight of thecomposition. Examples of adhesion promoters include phenolics, such asMETHYLON phenolic resin available from Occidental Chemicals, andorganosilanes, such as epoxy, mercapto or amino functional silanes, suchas SILQUEST® A-187 and SILQUEST® A-1100 available from MomentivePerformance Materials. Masking agents, such as pine fragrance or otherscents, which may be useful in masking any low level odor of thecomposition, may be present in an amount from 0.1 wt % to 1 wt %, basedon the total dry weight of the composition.

In certain embodiments, compositions provided by the present disclosuremay comprise a plasticizer that may facilitate the use ofsulfur-containing polymers having a higher glass transition temperature,T_(g), than would ordinarily be useful in an aerospace sealant. Forexample, use of a plasticizer may effectively reduce the T_(g) of acomposition, and thereby increase the low-temperature flexibility of thecured polymerizable composition beyond that which would be expected onthe basis of the T_(g) of the sulfur-containing polymers alone.Plasticizers suitable in certain embodiments of the compositionsinclude, for example, phthalate esters, chlorinated paraffins, andhydrogenated terphenyls. A plasticizer or combination of plasticizersmay constitute from 1 wt % to 40 wt % of a composition, or from 1 wt %to 10 wt % of a composition. In certain embodiments, a composition maycomprise one or more organic solvents, such as isopropyl alcohol, in anamount, for example, from 0 wt % to 15 wt %, from 0 wt % to 10 wt %, orfrom 0 wt % to 5 wt %, based on the non-dry weight of the composition.

In certain embodiments, compositions provided by the present disclosureare substantially free or, in some cases, completely free, of anysolvent, such as an organic solvent or an aqueous solvent, i.e., water.Stated differently, in certain embodiments, compositions provided by thepresent disclosure are substantially 100% solids.

In certain embodiments, compositions, such as sealant compositions, maybe provided as multi-pack compositions, such as two-pack compositions,wherein one package comprises one or more sulfur-containing polymersprovided by the present disclosure and a second package comprises one ormore curing agents for the one or more sulfur-containing polymers.Additives and/or other materials may be added to either package asdesired or necessary. The two packages may be combined and mixed priorto use. In certain embodiments, the pot life of the mixed polythioetherand curing agent is at least 30 minutes, at least 1 hour, at least 2hours, and in certain embodiments, more than 2 hours, where pot liferefers to the period of time the composition remains suitable for use asa sealant after mixing.

Compositions provided by the present disclosure may be applied to any ofa variety of substrates. Examples of substrates to which a compositionmay be applied include titanium, stainless steel, and aluminum, whichmay be anodized, primed, organic-coated or chromate-coated; epoxy;urethane; graphite; fiberglass composite; KEVLAR®; acrylics; andpolycarbonates.

Compositions provided by the present disclosure may be applied directlyonto the surface of a substrate or over an underlayer by any suitablecoating process known to those of ordinary skill in the art.

In certain embodiments, compositions provided by the present disclosureare fuel-resistant. As used herein, the term “fuel resistant” means thata composition, when applied to a substrate and cured, can provide acured product, such as a sealant, that has a percent volume swell of notgreater than 40%, in some cases not greater than 25%, in some cases notgreater than 20%, in yet other cases not more than 10%, after immersionfor one week at 140° F. (60° C.) and ambient pressure in Jet ReferenceFluid (JRF) Type I according to methods similar to those described inASTM D792 (American Society for Testing and Materials) or AMS 3269(Aerospace Material Specification. Jet Reference Fluid JRF Type I, asemployed for determination of fuel resistance, has the followingcomposition (see AMS 2629, issued Jul. 1, 1989, §3.1.1 etc., availablefrom SAE (Society of Automotive Engineers): toluene: 28±1% by volume;cyclohexane (technical): 34±1% by volume; isooctane: 38±1% by volume;and tertiary dibutyl disulfide: 1±0.005% by volume.

In certain embodiments, compositions provide a cured product, such as asealant, exhibiting an elongation of at least 100% and a tensilestrength of at least 400 psi when measured in accordance with theprocedure described in AMS 3279, §3.3.17.1, test procedure AS5127/1,§7.7.

In certain embodiments, compositions provide a cured product, such as asealant exhibits a lap shear strength of greater than 200 psi and insome cases at least 400 psi when measured according to the proceduredescribed in SAE AS5127/1 paragraph 7.8.

In certain embodiments, a cured sealant comprising a sulfur-containingpolymer provided by the present disclosure meets the requirements foraerospace sealants as set forth in AMS 3277.

Furthermore, methods are provided for sealing an aperture utilizing acomposition provided by the present disclosure. These methods comprise,for example, applying a composition provided by the present disclosureto a surface to seal an aperture; and curing the composition. In certainembodiments, a composition may be cured under ambient conditions, whereambient conditions refers to a temperature from 20° C. to 25° C. Incertain embodiments, a composition may be cured under conditionsencompassing a temperature from 0° C. to 100° C. and humidity from 0% RHto 100% RH. In certain embodiments, a composition may be cured at ahigher temperature such as at least 30° C., at least 40° C., and incertain embodiments, at least 50° C. In certain embodiments, acomposition may be cured at room temperature, e.g., 25° C. In certainembodiments, a composition may be cured upon exposure to actinicradiation such as ultraviolet radiation. As will also be appreciated,the methods may be used to seal apertures on aerospace vehicles.

EXAMPLES

Embodiments provided by the present disclosure are further illustratedby reference to the following examples, which describe the synthesis,properties, and uses of certain sulfur-containing polymers. It will beapparent to those skilled in the art that many modifications, both tomaterials, and methods, may be practiced without departing from thescope of the disclosure.

Example 1 Sulfur-Containing Polymer Synthesis

Thiodiglycol (549.84 g), paraformaldehyde (95% purity) (150.40 g),dithiodiglycol (77.1 g), AMBERLYST® 15 (107.7 g, Dow Chemical Company),and toluene (1,000 mL) were charged in a 2-liter, 4-neck, round-bottomflask. The flask was equipped with a heating mantle, thermocouple,temperature controller, and a Dean-Stark adapter fitted with a refluxcondenser, dropping funnel, and inlet for nitrogen positive pressure.The reactants were stirred under a nitrogen atmosphere, heated to 118°C., and maintained at 118° C. for about 9 h. During this period,collected water was periodically removed from the Dean-Stark adapter.The reaction mixture was then cooled to room temperature and filteredwith suction through a coarse-fitted Buchner funnel (600 mL volume) witha 9.0 cm-diameter Whatman GF/A filter paper over the frit. The flask andfilter cake were washed with 500 mL toluene. A filtrate was obtained.The filtrate was dried in vacuo using a 2-L, round bottomed flask(rotary evaporator, 7 torr final vacuum, 90° C. water bath). A yellow,viscous polymer (529.8 g) was obtained. The sulfur-containing polymerhad a hydroxyl number of 15.8 and a viscosity of 386 poise.

Example 2 Sulfur-Containing Polymer Synthesis

Thiodiglycol (1,832.79 g), paraformaldehyde (95% purity) (360.4 g),AMBERLYST® 15 (319.1 g, Dow Chemical Company), and toluene (1,000 mL)were charged in a 5-liter 4-neck round-bottom flask. The flask wasequipped with a heating mantle, thermocouple, temperature controller,and a Dean-Stark adapter fitted with a reflux condenser, droppingfunnel, and inlet for nitrogen positive pressure. The reactants werestirred under a nitrogen atmosphere, heated to 118° C., and maintainedat 118° C. for about 7 h. During this period, collected water wasperiodically removed from the Dean-Stark adapter. The reaction mixturewas then cooled to room temperature and filtered with suction through acoarse-fritted Buchner funnel (600 mL volume) with a 9.0 cm-diameterWhatman GF/A filter paper over the frit. The flask and filter cake werewashed with 500 mL toluene. A filtrate was obtained. The filtrate wasdried in vacuo using a 2-L, round bottomed flask (rotary evaporator, 7ton final vacuum, 90° C. water bath). A yellow, viscous polymer (1,455.8g) was obtained. The sulfur-containing polymer had a hydroxyl number of34.5 and a viscosity of 92 poise.

Example 3 Acrylate-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer of Example 2 (164.3 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of isocyanatoethyl methacrylate (10.1 g) and a0.01% solution of dibutyltin dilaurate dissolved in methyl ethyl ketone(1.7 g). The reaction mixture was maintained at 76.6° C. for 5 h andthen cooled to room temperature. A 1% solution of benzoyl chloridedissolved in methyl ethyl ketone (1.8 g) was then added to the reactionmixture. The resulting polymer had a viscosity of 177 poise.

Example 4 Allyl-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer in Example 2 (143.1 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of allyl isocyanate (4.8 g) and a 0.01%solution of dibutyltin dilaurate dissolved in methyl ethyl ketone (1.5g). The reaction mixture was maintained at 76.6° C. for 5 h and thencooled to room temperature. The resulting polymer had a viscosity of 176poise.

Example 5 TMI-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer in Example 2 (150.9 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of 3-isopropenyl-α,α-dimethylbenzyl isocyanate(12.7 g, available from Cytec Industries) and a 0.01% solution ofdibutyltin dilaurate dissolved in methyl ethyl ketone (1.63 g). Thereaction mixture was maintained at 76.6° C. for 6 hours and then cooledto room temperature. The resulting polymer had a viscosity of 291 poise.

Example 6 Curing of Acrylate-Terminated Sulfur-Containing Polymer

The curing reaction was carried out in a 100 g plastic containerequipped with a lid. The acrylate-terminated sulfur-containing polymerof Example 3 (40.8 g) and Irgacure® 2022 (0.2 g, 0.5% by weight, BASF)were mixed by hand in the container. The container was then placed in aspeed mixer (DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymerwas poured over a circular (5 in-diameter) metal lid (pre-treated withValspar Mold Release 225), and placed under ultraviolet (UV) radiationfor 15 sec, after which time the polymer had completely cured. A SuperSix curing unit (Fusion Systems Inc.) was used to provide the UVradiation. The curing unit was equipped with a 300 W H-bulb, whichproduced UV wavelengths ranging from 200 nm to 450 nm. A total dosage of3.103 J/cm² UV energy, measured using a UV power puck (EIT, Inc.,Sterling, Va.) was applied to the polymer composition. Up to 2 inches ofcured polymer was obtained. The hardness of the polymer was measuredwith a durometer to be 32 Shore A. Hardness data was obtained accordingto ASTM D 2240.

Example 7 Curing of TMI-Terminated Sulfur-Containing Polymer

The curing reaction was performed in a 100 g plastic container equippedwith a lid. The TMI-terminated sulfur-containing polymer described inExample 5 (40.8 g) and IRGACURE® 2022 (0.2 g, 0.5% by weight) were mixedby hand in the container. The container was then placed in a speed mixer(DAC 600 FVZ) and mixed for 1 min at 2,300 rpm. The polymer was pouredover a circular (5 inch-diameter) metal lid (pre-treated with ValsparMold Release 225), and placed under UV light for 15 sec. A Super Sixcuring unit (Fusion Systems Inc.) was used to provide the UV radiation.The curing unit was equipped with a 300 W H-bulb, which produced UVwavelengths ranging from 200 nm to 450 nm. A total dosage of 3.103 J/cm²UV energy, measured using a UV power puck (EIT, Inc., Sterling, Va.) wasapplied to the polymer composition. Up to 2 mm of cured polymer wasobtained.

Example 8 Silyl-terminated Sulfur-Containing Polymer

The sulfur-containing polymer of Example 2 (151.5 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, and an inlet for nitrogen positivepressure, mechanical stirrer (PTFE paddle and bearing). The polymer wasstirred at ca. 200 rpm and heated to 76.6° C. (170° F.), followed by theaddition of SILQUEST®A-Link 25 (23.1 g, Momentive Performance Materials)and a 0.01% solution of dibutyltin dilaurate dissolved in methyl ethylketone (2.8 g). The reaction mixture was maintained at 76.6° C. for 5 hand then cooled to room temperature. The resulting polymer had aviscosity of 80 poise.

Example 9 Silyl-Terminated Sulfur-Containing Polymer

The sulfur-containing polymer of Example 2 (162.3 g) was charged into a500-mL, 4-neck round-bottom flask. The flask was equipped with a mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer (PTFE paddle and bearing). Thepolymer was stirred at ca. 200 rpm and heated to 76.6° C. (170° F.),followed by the addition of SILQUEST® A-Link 35 (20.6 g, MomentivePerformance Materials) and a 0.01% solution of dibutyltin dilauratedissolved in methyl ethyl ketone (1.8 g). The reaction mixture wasmaintained at 76.6° C. for 5 h and then cooled to room temperature. A 1%solution of benzoyl chloride dissolved in methyl ethyl ketone (1.8 g)was then added to the reaction mixture. The resulting polymer had aviscosity of 114 poise.

Example 10 Sealant Composition: Silyl-Terminated Sulfur-ContainingPolymer

A sealant composition was prepared by mixing the silyl-terminatedsulfur-containing polymer described in Example 8 and other ingredientsdescribed in Table 1.

TABLE 1 Sealant Composition Charge Weight, Component grams Polymer fromExample 8 35 Carbon Black 15 Plasticizer¹ 2 Metacure T-12² 0.5¹Available from Solvay. ²Available from Air Products and Chemicals, Inc.

After mixing, the composition was sealed in a moisture-free containerand allowed to stand in the moisture-free container for approximatelyone month at ambient conditions. After storing for one month, thecontainer was opened exposing the polymer to the ambient environment tocure the polymer. Hardness measurements were taken periodically using aRex Durometer according to ASTM D2240. In addition, cured samples wereimmersed in Jet Reference Fuel (JRF) Type I for 7 days at 140° F. Afterimmersion, volume swell percentage and percent weight loss of the curedsample were measured according to SAE AS5127/1 section 7.4. The resultsare presented in Tables 2 and 3.

TABLE 2 Curing Time vs. Hardness Hardness, Cure Time Shore A 60 days 70

TABLE 3 Volume Swell and Weight Loss After JRF Immersion Average VolumeSwell, Average Weight Loss, Sealant Composition % % Example 10/Table 18.14 2.13

Example 11 Sealant Composition: Silyl-Terminated Sulfur-ContainingPolymer

A sealant composition was prepared by mixing the silyl-terminatedsulfur-containing polymer described in Example 9 and other ingredientsdescribed in Table 4.

TABLE 4 Sealant Composition Charge Weight, Component grams Polymer fromExample 9 35 Carbon Black 15 Plasticizer 2 Metacure T-12 0.5

After mixing, the composition was then sealed in a moisture-freecontainer and allowed to stand in moisture-free conditions forapproximately one month at ambient conditions. After one month ofstorage, the container was opened the polymer exposed to the ambientenvironment (room temperature and humidity) to cure the polymer.Hardness measurements were taken periodically using a Rex Durometeraccording to ASTM D2240. In addition, cured samples were immersed in JetReference Fuel (JRF) Type I for 7 days at 140° F. After immersion,volume swell percentage and percent weight loss of a cured sample weremeasured according to SAE AS5127/1 section 7.4. The results arepresented in Tables 5 and 6.

TABLE 5 Curing Time vs. Hardness Hardness, Cure Time Shore A 48 hr 25 3days 43 4 days 49 30 days 63

TABLE 6 Volume Swell and Weight Loss After JRF Immersion Average VolumeSwell, Average Weight Loss, Sealant Composition % % Table 4 8.43 1.86

Example 12 Thiol-Terminated Sulfur-Containing Polymer

Dimercaptodioxaoctane (2.0 g, dissolved in 40 mL toluene) and1,8-diazabicyclo-[5,4,0]undec-7-ene (DBU) (0.03 g, available from AirProducts and Chemicals) were charged into a 300-mL 4-neck round-bottomflask. The flask was equipped with a mantle, thermocouple, temperaturecontroller, an inlet for nitrogen positive pressure, and a mechanicalstirrer (PTFE paddle and bearing). The mixture was stirred at ca. 200rpm and the acrylate-terminated sulfur-containing polymer of Example 3(54.6 g, dissolved in 40 ml toluene) was added drop-wise to the flask.The reaction mixture was heated to 100° C. and maintained at 100° C. for10 h. Toluene was then removed from the reaction mixture under vacuum.The resulting polymer had a mercaptan equivalent weight of 5,129 and aviscosity of 201 poise.

Example 13 Thiol-Terminated Sulfur-Containing Polymer

Dimercaptodioxaoctane (4.06 g), the acrylate-terminatedsulfur-containing polymer of Example 3 (93.6 g), and VAZO®-67 (1.1 g,available from Dupont) were charged into a 500-mL, 4-neck round-bottomflask. The flask was equipped with a mantle, thermocouple, temperaturecontroller, an inlet for nitrogen positive pressure, and a mechanicalstirrer (PTFE paddle and bearing). The mixture was stirred at ca. 200rpm and heated to 80° C. and maintained at 80° C. for 15 h. AdditionalVAZO®-67 (1.0 g) was charged to the reaction mixture during thereaction. The resulting polymer had a mercaptan equivalent weight of4,834 and a viscosity of 299 poise.

Example 14 Performance Data for Thiol-Terminated Sulfur-ContainingPolymer of Example 12

The curing reaction was performed in a 100 g plastic container equippedwith a lid. The thiol-terminated sulfur-containing polymer described inExample 13 (51.3 g), diethylene glycol divinyl ether (7.91 g), andIRGACURE® 2022 (0.30 g, 0.5% by weight) were mixed by hand in thecontainer. The container was then placed in a speed mixer (DAC 600 FVZ)and mixed for 1 min at 2,300 rpm. The polymer was poured over a circular(5 inch-diameter) metal lid (pre-treated with Valspar Mold Release 225),and placed under UV light for 15 sec, after which time the polymer hadcompletely cured. A Super Six curing unit (Fusion Systems Inc.) was usedto provide the UV radiation. The curing unit was equipped with a 300 WH-bulb, which produced UV wavelengths ranging from 200 nm to 450 nm. Atotal dosage of 3.103 J/cm² UV energy, measured using a UV power puck(EIT, Inc., Sterling, Va.) was applied to the polymer composition.

Example 15 Sulfur-Containing Polymer Reaction with MethylMercaptoacetate

The sulfur-containing polymer of Example 2 (89.6 g), methylmercaptoacetate (21.4 g) and sodium methoxide (0.4 g) were charged intoa 300-mL, 3-neck round-bottom flask. The flask was equipped with amantle, thermocouple, temperature controller, mechanical stirrer (PTFEpaddle and bearing), and a Dean-Stark trap connected to a refluxcondenser and topped with an inlet for nitrogen positive pressure. Themixture was heated to 150° C. and stirred at 300 rpm. The mixture wasmaintained at 150° C. for 48 h. The solvent was removed at 150° C. undervacuum for 1.4 h. The resulting polymer had a viscosity of 41 poise anda mercaptan equivalent weight of 6,934.

Example 16 Sulfur-Containing Polymer Reaction with Mercaptoacetic Acid

The sulfur-containing polymer of Example 2(89.6 g), mercaptoacetic acid(13.8 g), hafnium chloride-THF complex (HfCl₄.2THF, 1.20 g, availablefrom Aldrich) and toluene (75 mL) were charged into a 300-mL, 3-neckround-bottom flask. The flask was equipped with a mantle, thermocouple,temperature controller, mechanical stirrer (PTFE paddle and bearing),and a Dean-Stark trap connected to a reflux condenser and topped withinlet for nitrogen positive pressure. The mixture was heated to 130° C.and stirred at 300 rpm. The mixture was maintained at 130° C. for 18 h.NaHCO₃ (12.8 g) was then added to the reaction mixture to consume excessmercaptoacetic acid while stirring briefly for 4 min. The product wasfiltered through a Buchner funnel with Whatman GF/A paper (7.0 cm dia.)and thoroughly washed with 100 mL toluene. The resulting filtrate wasstripped in vacuo (rotary evaporator, 90° C. water bath, <5 torr finalvacuum) to afford 90.1 g of a viscous polymer having a viscosity of 52poise and a mercaptan equivalent weight of 4,223.

Example 17 Polyformal Polymer Reaction with TDI and Mercaptopropanol

The sulfur-containing polymer of Example 2 (89.6 g) and toluenediisocyanate (17.5 g) were charged into a 300-mL, 3-neck round-bottomflask. The flask was equipped with a mantle, thermocouple, temperaturecontroller, mechanical stirrer (PTFE paddle and bearing), and a nitrogeninlet. The mixture was heated to 71° C. and stirred at 200 rpm andmaintained at 71° C. for 27 h. 3-Mercaptopropanol (7.9 g) was then addedand the reaction mixture was heated to 77° C. and stirred at 200 rpm for41 h. Finally, the reaction mixture was heated to 100° C. under vacuumfor 30 min to remove unreacted 3-mercaptopropanol. The resulting polymerhad a mercaptan equivalent weight of 2,630.

Example 18 Epoxy Terminated Sulfur-Containing Polymer

Sodium hydride 60% dispersion in mineral oil (Aldrich) (1.92 g) wascharged to a 4-neck round bottom flask equipped with a heating mantle,thermocouple, temperature controller, an inlet for nitrogen positivepressure, and a mechanical stirrer, and blanketed with nitrogen. Thedispersion was washed three times with 5 mL heptanes. The reaction wasstirred at room temperature, followed by the addition of a premixedsolution of sulfur-containing polymer of Example 2 (157.08 g) and drydimethylsulfoxide (312 g) over 45 minutes. The reaction was stirred atca. 200 rpm for 4 hours and epichlorohydrin (11.10 g) (Aldrich) wasadded dropwise while the reaction was allowed to exotherm to 50° C. Thereaction was held for 2 hours at 50° C., cooled to room temperature, andstirred overnight. The solution was then poured into 1,100 g of waterand extracted twice with methylene chloride, washed with a saturatedaqueous solution of NaCl, and dried over sodium sulfate. The solvent wasremoved under vacuum to provide a light brown oil with an epoxyequivalent wt of 1,960 g/mlq.

Finally, it should be noted that there are alternative ways ofimplementing the embodiments disclosed herein. Accordingly, the presentembodiments are to be considered as illustrative and not restrictive.Furthermore, the claims are not to be limited to the details givenherein, and are entitled their full scope and equivalents thereof.

What is claimed is:
 1. A terminal-modified sulfur-containing polymer ofFormula (II):

wherein: n is an integer selected from 2 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; each R² is independently selected from hydrogen and C₁₋₆alkyl; and each R³ comprises a terminal thiol-terminated group.
 2. Theterminal-modified sulfur-containing polymer of claim 1, wherein, n is aninteger selected from 2 to 50; each p is 1; each R¹ is independentlyselected from ethane-1,2-diyl; and each R² is hydrogen.
 3. Theterminal-modified sulfur-containing polymer of claim 1, wherein each R³is a thiol-terminated group and is independently selected from a groupof Formula (o), Formula (p), Formula (q), Formula (r), Formula (s),Formula (t), Formula (u), and Formula (v):

wherein: each R⁶ is selected from a moiety derived from a diisocyanateand a moiety derived from an ethylenically unsaturated monoisocyanate;each R⁷ is selected from C₂₋₁₄ alkanediyl and C₂₋₁₄ heteroalkanediyl;and each R⁹ is selected from C₂₋₆ alkanediyl, C₂₋₆ heteroalkanediyl,C₆₋₁₂ arenediyl, substituted C₆₋₁₂ arenediyl, C₆₋₁₂ heteroarenediyl,substituted C₆₋₁₂ heteroarenediyl, C₃₋₁₂ cycloalkanediyl, substitutedC₃₋₁₂ cycloalkanediyl, C₃₋₁₂ heterocycloalkanediyl, substituted C₃₋₁₂heterocyclo alkanediyl, C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈heteroalkanearenediyl, C₄₋₁₈ alkanecycloalkanediyl, and substitutedC₄₋₁₈ alkanecyclo alkanediyl.
 4. The terminal-modified sulfur-containingpolymer of claim 3, wherein, each R³ is a group of Formula (o); and eachR⁶ is a group derived from a diisocyanate.
 5. The terminal-modifiedsulfur-containing polymer of claim 4, wherein the diisocyanate isselected from 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate,2,6-toluene diisocyanate (2,6-TDI), 2,4-toluene diisocyanate (2,4-TDI),a blend of 2,4-TDI and 2,6-TDI, 1,5-diisocyanato naphthalene, diphenyloxide 4,4′-diisocyanate, 4,4′-methylenediphenyl diisocyanate (4,4-MDI),2,4′-methylenediphenyl diisocyanate (2,4-MDI),2,2′-diisocyanatodiphenylmethane (2,2-MDI), diphenylmethane diisocyanate(MDI), 3,3′-dimethyl-4,4′-biphenylene isocyanate,3,3′-dimethoxy-4,4′-biphenylene diisocyanate,1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methyl benzene,2,4,6-triisopropyl-m-phenylene diisocyanate, and 4,4-methylenedicyclohexyl diisocyanate (H₁₂MDI).
 6. The terminal-modifiedsulfur-containing polymer of claim 3, wherein, each R³ is a group ofFormula (o); and each R⁶ is a group derived from an ethylenicallyunsaturated monoisocyanate.
 7. The terminal-modified sulfur-containingpolymer of claim 6, wherein the unsaturated monoisocyanate is2-isocyanatoethyl methacrylate.
 8. The terminal-modifiedsulfur-containing polymer of claim 3, wherein, each R³ is selected froma group of Formula (o), Formula (p), Formula (q), Formula (s), Formula(t), Formula (u), and Formula (v); and each R⁷ is selected from C₂₋₆alkanediyl.
 9. The terminal-modified sulfur-containing polymer of claim3, wherein, each R³ is selected from a group of Formula (o), Formula(p), Formula (q), Formula (s), Formula (t), Formula (u), and Formula(v); and each R⁷ is selected from —CH₂—S—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—,—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—, and —(CH₂)₂—S—(CH₂)₂—O—(CH₂)₂—O—(CH₂)₂—. 10.The terminal-modified sulfur-containing polymer of claim 3, wherein,each R³ is selected from a group of Formula (t) and Formula (u); andeach R⁹ is selected from C₂₋₆ alkanediyl, C₆₋₁₂ arenediyl, substitutedC₆₋₁₂ arenediyl, C₃₋₁₂ cycloalkanediyl, substituted C₃₋₁₂cycloalkanediyl, C₇₋₁₈ alkanearenediyl, substituted C₇₋₁₈alkanearenediyl, C₄₋₁₈ alkanecycloalkanediyl, and substituted C₄₋₁₈alkanecycloalkanediyl.
 11. The terminal-modified sulfur-containingpolymer of claim 3, wherein, each R³ is a group of Formula (v); and eachR⁷ is —(CH₂)₂—S—CH₂— O—(CH₂)₂—O—CH₂— SH.
 12. The terminal-modifiedsulfur-containing polymer of claim 1, wherein the thiol-terminatedsulfur-containing polymer is selected from a polymer of Formula (IVa)and a polymer of Formula (IVb):

wherein n is an integer selected from 2 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; each R² is independently selected from hydrogen, C₁₋₆ alkyl,C₇₋₁₂ phenylalkyl, substituted₇₋₁₂ phenylalkyl, C₆₋₁₂ cycloalkylalkyl,substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂ cycloalkyl, substituted C₃₋₁₂cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl; and each R⁶ isindependently selected from C₂₋₆ alkanediyl and C₅₋₁₂ heteroalkanediyl.13. The terminal-modified sulfur-containing polymer of claim 12, whereineach p is
 1. 14. The terminal-modified sulfur-containing polymer ofclaim 12, wherein each R¹ is selected from C₂₋₅ alkanediyl.
 15. Theterminal-modified sulfur-containing polymer of claim 12, wherein each R¹is ethane-1,2-diyl.
 16. The terminal-modified sulfur-containing polymerof claim 12, wherein, each R¹ is selected from ethane-1,2-diyl andpropane-1,3-diyl; each R² is selected from hydrogen, methyl, and ethyl;and each R⁶ is selected from ethane-1,2-diyl and propane-1,3-diyl. 17.The terminal-modified sulfur-containing polymer of claim 12, wherein nis an integer from 5 to
 40. 18. A terminal-modified sulfur-containingpolymer comprising the reaction products of reactants comprising (a) and(b), wherein, (a) comprises the reaction products of reactants (i) and(ii), wherein, (i) comprises a sulfur-containing polymer of Formula (I):

wherein: n is an integer selected from 2 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; and each R² is independently selected from hydrogen, C₁₋₆alkyl, C₇₋₁₂ phenylalkyl, substituted C₇₋₁₂ phenylalkyl, C₆₋₁₂cycloalkylalkyl, substituted C₆₋₁₂ cycloalkylalkyl, C₃₋₁₂ cycloalkyl,substituted C₃₋₁₂ cycloalkyl, C₆₋₁₂ aryl, and substituted C₆₋₁₂ aryl;and (ii) comprises a first compound selected from a diisocyanate,thiourea, an ethylenically unsaturated isocyanate, and a tosylate; and(b) comprises a mercaptoalkanol when (ii) comprises a diisocyanate; (b)comprises a metal hydrosulfide when (ii) comprises thiourea; (b)comprises a dithiol when (ii) comprises an ethylenically unsaturatedisocyanate; and (b) comprises a metal hydrosulfide when (ii) comprises atosylate.
 19. The terminal-modified sulfur-containing polymer of claim18, wherein, each R¹ is independently selected from ethane-1,2-diyl; andeach R² is hydrogen.
 20. The terminal-modified sulfur-containing polymerof claim 18, wherein the sulfur-containing polymer of Formula (I)comprises the reaction products of: (i) a sulfur-containing diol; and(ii) a reactant selected from an aldehyde, ketone, and a combinationthereof.
 21. The terminal-modified sulfur-containing polymer of claim20, wherein the sulfur-containing diol is selected from2,2′-thiodiethanol, 3,3′-thiobis(propan-1-ol), 4,4′-thiobis(butan-1-ol),and a combination of any of the foregoing.
 22. The terminal-modifiedsulfur-containing polymer of claim 20, wherein (ii) is an aldehyde andcomprises formaldehyde.
 23. The terminal-modified sulfur-containingpolymer of claim 20, wherein, the diol comprises 2,2′-thiodiethanol; andthe reactant comprises formaldehyde.
 24. The terminal-modifiedsulfur-containing polymer of claim 18, wherein the sulfur-containingpolymer of Formula (I) has a hydroxyl number from 10 to
 100. 25. Theterminal-modified sulfur-containing polymer of claim 18, wherein, eachR¹ is the same and is selected from ethane-1,2-diyl andpropane-1,3-diyl; and each R² is independently selected from hydrogen,methyl, and ethyl.
 26. The terminal-modified sulfur-containing polymerof claim 18, wherein each R¹ is the same and is ethane-1,2-diyl.
 27. Theterminal-modified sulfur-containing polymer of claim 18, wherein n is aninteger selected from 7 to
 30. 28. The terminal-modifiedsulfur-containing polymer of claim 18, wherein, the diisocyanatecomprises a diisocyanate selected from 1,3-phenylene diisocyanate,1,4-phenylene diisocyanate, 2,6-toluene diisocyanate (2,6-TDI),2,4-toluene diisocyanate (2,4-TDI), a blend of 2,4-TDI and 2,6-TDI,1,5-diisocyanato naphthalene, diphenyl oxide 4,4′-diisocyanate,4,4′-methylenediphenyl diisocyanate (4,4-MDI), 2,4′-methylenediphenyldiisocyanate (2,4-MDI), 2,2′-diisocyanatodiphenylmethane (2,2-MDI),diphenylmethane diisocyanate (MDI), 3,3′-dimethyl-4,4′-biphenyleneisocyanate, 3,3′-dimethoxy-4,4′-biphenylene diisocyanate,1-[(2,4-diisocyanatophenyl)methyl]-3-isocyanato-2-methyl benzene,2,4,6-triisopropyl-m-phenylene diisocyanate, and 4,4-methylenedicyclohexyl diisocyanate (H₁₂MDI); the ethylenically unsaturatedmonoisocyanate is selected from vinyl isocyanate, allyl isocyanate,3-isocyanato-2-methyl-2-propene, methacryloyl isocyanate,isocyanatoethyl methacrylate, vinyl-benzyl isocyanate,3-isocyanato-1-butene, 3-isocyanato-3-methyl-1-butene,4-isocyanato-2-methyl-1-butene, 4-isocyanato-3,3-dimethyl-1-butene,4-isocyanato-4-methyl-1-pentene, and 5-isocyanato-1-pentene,2-isocyanatoethyl methacrylate, and dimethyl-meta-isopropenylbenzylisocyanate (TMI)methacrylate; and the tosylate comprises sulfonylchloride.
 29. The terminal-modified sulfur-containing polymer of claim18, wherein, the mercaptoalkanol comprises a mercaptoalkanol selectedfrom 2-mercaptoethan-1-ol, 3-mercaptopropan-1-ol, 4-mercaptobutan-1-ol,5-mercaptopentan-1-ol, and 6-mercaptohexan-1-ol; the metal hydrosulfidecomprises sodium hydrosulfide; and the dithiol comprises a dithiolselected from 1,2-ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol,1,3-butanedithiol, 1,4-butanedithiol, 2,3-butanedithiol,1,3-pentanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol,1,3-dimercapto-3-methylbutane, dipentenedimercaptan,ethylcyclohexyldithiol, dimercaptodiethylsulfide, methyl-substituteddimercaptodiethylsulfide, dimethyl-substituted dimercaptodiethylsulfide,dimethyl-substituted dimercaptodiethylsulfide, dimercaptodioxaoctane,and 1,5-dimercapto-3-oxapentane.
 30. A composition comprising theterminal-modified sulfur-containing polymer of claim
 1. 31. Thecomposition of claim 30 formulated as a sealant.
 32. A cured sealantcomprising the composition of claim
 31. 33. A method of sealing asubstrate comprising: applying the composition of claim 31 to asubstrate; and curing the composition to seal the substrate.
 34. Aterminal-modified sulfur-containing polymer of Formula (II):

wherein: n is an integer selected from 2 to 50; each p is independentlyselected from 1 and 2; each R¹ is independently selected from C₂₋₆alkanediyl; each R² is independently selected from hydrogen and C₁₋₆alkyl; and each R³ comprises a terminal silyl-terminated group.
 35. Theterminal-modified sulfur-containing polymer of claim 34, wherein, n isan integer selected from 2 to 50; each p is 1; each R¹ is independentlyselected from ethane-1,2-diyl; and each R² is hydrogen.
 36. Theterminal-modified sulfur-containing polymer of claim 34, wherein each R³comprises a silyl-terminated group and is independently selected from agroup of Formula (f), and Formula (g):

wherein, each R⁶ is derived from an ethylenically unsaturatedmonoisocyanate; each R¹⁰ is independently selected from C₁₋₆ alkyl, C₁₋₆alkoxy, C₅₋₆ cycloalkyl, C₆₋₁₂ cycloalkylalkyl, phenyl, and C₇₋₁₂phenylalkyl; wherein at least one R¹⁰ is C₁₋₆ alkoxy; and each R¹¹ isC₁₋₆ alkanediyl.
 37. The terminal-modified sulfur-containing polymer ofclaim 36, wherein each R¹⁰ is selected from methoxy, ethoxy, andpropoxy.
 38. The terminal-modified sulfur-containing polymer of claim36, wherein the silyl-terminal group is selected from a trialkoxysilane,a dialkoxysilane, and a monoalkoxysilane.
 39. The terminal-modifiedsulfur-containing polymer of claim 36, wherein, each R³ comprises asilyl-terminated group of Formula (g); and each R¹¹ is selected frommethane-diyl, ethane-1,2-diyl, and propane-1,2-diyl.
 40. A compositioncomprising the terminal-modified sulfur-containing polymer of claim 34.41. The composition of claim 40 formulated as a sealant.
 42. A curedsealant comprising the composition of claim
 41. 43. A method of sealinga substrate comprising: applying the composition of claim 41 to asubstrate; and curing the composition to seal the substrate.